Energy Conversion Device and Method for Making and Using Same

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Patent Application Publication May 19, 2016 Sheet 13 of 18 US 2016/0141533 A1

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Direction of Axes for Linear Molecular CXCXY Stacks

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ENERGY CONVERSION DEVICE AND which require more energy than is available in a 1.8 eV METHOD FOR MAKING AND USING SAME photon (visible light). The EPWASER process mechanism represents, according to one embodiment of the invention, a

CROSS-REFERENCE TO RELATED practical approach to high efficiency Solar-powered decom APPLICATIONS position of water. The EPWASER effect can be produced not 0001. The present application is a (bypass) continuation only in Solid state, but also in vitro, and can serve as the basis application of co-pending International Application No. for a practical Solar energy converter, in general. PCT/US2014/030670, filed Mar 17, 2014, which was pub SUMMARY OF THE INVENTION

claims the right of priority based on Provisional Application 0005 According to one aspect of the present invention, No. 61/801,647, filed Mar. 15, 2013. there has been provided an energy conversion device, com prising: a fabricated and ordered ensemble of a material com

BACKGROUND OF THE INVENTION prised of atoms and/or molecules that can store input energy in the form of electrons elevated to an increased level of 0002 The present invention relates to an energy conver excitement, wherein the ordered ensemble of material exhib sion device and to a method for utilizing same and also for its, between adjacent atoms or molecules, a relative binding making same. More particularly the invention relates to an energy for an excited electron that is sufficient to render the apparatus and a method for employing energy from an elec material capable of a spin-allowed transfer of an excited tron- and, optionally, photon-containing energy wave that is electron to an adjacent atom or molecule in the ensemble to induced in one or more aggregated molecular ensembles, form a meta-stable configuration in which the excited elec wherein the emission of which is stimulated from the tron is spin-forbidden to lose its energy within the atom or ensembles. Stimulation can be accomplished by a wide vari molecule to which it has moved, and wherein the ordered ety of energy inputs and is preferably accomplished by pho ensemble of material is likewise capable of releasing stored ton energy, in one preferred aspect of the invention, by Solar energy by means of a charge transfer between adjacent atoms energy. The energy derived from this electron and/or photon or molecules from an excited electron state to a lower state in energy wave is useful for providing energy that can be used the adjacent atom or molecule, in a manner that Sums up a for a large number of purposes, including: modulation of plurality of individual excitations in an output for the device. signals in circuits used for communication purposes (in the 0006. The invention also provides a method for fabricating broadest sense), e.g., in optical fibers, electronic conductors energy conversion devices as defined above. or radio transmission systems; performing chemical reduc 0007. In accordance with another aspect of the invention, tion reactions, by themselves, or in favorably shifting or driv there is provided a method of enhancing the intensity of ing the energy equilibrium of other types of chemical reac electromagnetic energy, comprising: exposing to a source of tions; and performing as an energy conversion device, e.g., as electromagnetic energy, a fabricated and ordered ensemble of a photovoltaic energy converter. Although differing from a a material as defined in claim 1, wherein the source of elec laser by virtue its production of inter alia, a charge transfer tromagnetic energy is Sufficient to raise electrons in the com rather than merely light, the device of the invention can be pound to an elevated level of excitement to Such a degree that employed in virtually all of the same fields in which a laser is a population inversion occurs, wherein the number of mol utilized, such as communications, data storage, etc. ecules in the excited States is greater than the number of 0003. Our research has led to the discovery of a novel molecules in the lower energy states; and releasing stored mechanism to explain the conversion of energy, including energy by means of a charge transfer between adjacent atoms light energy. The present invention involves a mechanism or or molecules from an excited electron state to a lower state in process denominated as Electron Polarization Wave Ampli the adjacent atom or molecule, in a manner that Sums up a fied by Stimulated Emission of Radiation (EPWASER is an plurality of individual excitations in an output. Preferably, the acronym). The process, which results in the formation of an ordered ensemble comprises an ordered structure of atoms or electron-containing energy wave in aggregated molecular molecules arranged close together so that the quantum ensembles, is Summarized as follows, with respect to one type mechanical probability of location for excited electrons in a of suitable molecule, for example, but not limited to chloro given unit overlaps into the location of adjacent neighboring phyll. A quantum mechanical model shows that in certain units.

closely associated groups of molecules, like chlorophyll. 0008 According to another preferred aspect of the inven light absorption can lead to electron transfer between adja tion, the method further comprises applying the energy cent molecules. This type of inter-molecular electron transfer release to a chemical reaction, more preferably a reaction will populate a metastable state such as the chlorophyll triplet comprising splitting water molecules into hydrogen and oxy state, which is normally spin-forbidden in isolated molecules. gen. In this and other preferred aspects of the invention, the Successive photon induced electron transfers can thus create application of the energy release is preferably to a photo a localized population inversion. In the stimulated emission chemical process, which requires energy steps greater than process, electrons return to the ground State of an adjacent the energy contained in one photon of light. molecule. This occurs because the decay of the triplet state is 0009. According to another aspect of the invention, the spin-forbidden within a given molecule. The EPWASER pro method uses, as the ordered ensemble of molecules, one cess results in the wave-like movement of electron-hole pairs comprising atomic or molecular ring compounds, especially (and optionally photons) which sum up or collate the energy those based on ring compounds having atomic units that area stored in the entire molecule ensemble. multiple of 4 and having conjugated double bonds in the ring. 0004. The energy charges produced by EPWASER action In preferred aspects, the ring compounds are based on a can be used in an endless number applications, including the porphyrin ring, especially chlorophyll. In other preferred participation in chemical reactions, such as water splitting, aspects of the invention, the ordered ensemble comprises a

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semiconductor material arranged to form a PN junction 0020 Some examples of an electron reflector include: (a.) region of a semiconductor diode, whereby when low Voltage localized magnetic field with a strong gradient e.g., field lines electric current is driven through the junction region in a converging to focal point; (b.) a high barrier. Such as a high direction at right angle to the axes of the ensemble electrons Voltage, to reflect an electron in one dimensional travel; or c. are pumped into excited States of the molecules or atoms and a wide barrier, Such as 20 molecules in a row, that are specifi energy produced by this pumping action is released in the cally designed to be high and wide enough to reflect the form of coherent charge transport along axis of the ensemble. electron back. For example, in the case of the last item, a set 0010 Preferred applications of the present device and/or of molecules can be put at the end of a stack that would only method comprise: allow the electron to pass if its energy was high enough to 0.011 conversion of photovoltaic energy; applying cur surmount the potential barrier. In this case the electrons rents caused by charge transfer for modulating signals in energy would have to be at least a minimum value in order to circuits employed for communication, wherein the commu climb the barrier and escape. An example of using this effect nication circuits comprise an optical fiber, an electric conduc to achieve a particular result would be to have barriers at both tor, or a radio transmission system; ends of the stack, with one end consisting of 20 molecules, 0012 utilizing the released energy stimulated from the and the other only 12 molecules. High energy electrons would stored energy to imprint a pattern to store information con only exit from the 12 molecule end, and the number of mol tent; ecules could be tailored to achieve the appropriate energy. 0013 storing the information is stored directly in the The energy of the electron would not be reduced once out, it excited energy states of the atomic or molecular units of the would only begated by the barrier. This new type of electronic ensemble, whereby some selected units in a chain are pumped device that only allows current flow when the electrons have to store excited electrons, while other selected units remain in sufficient energy, would be helpful in a solar collector where their lower energy states in Such a way that the pattern of the power conversion devices are designed to operate on excited vs. de-excited units becomes a form of encoded infor current with a particular Voltage potential. Current that was mation. A method of retrieving the encoded information from not of sufficient potential would be recycled until it was of Such a device comprises reading the variations of current that sufficient potential.

would be produced when the information ensemble releases 0021. According to another preferred aspect of the inven its stored energy by producing a modulated transport through tion, there is provided an apparatus for carrying out a chemi the chain of selectively pumped and de-excited units: cal reaction, comprising: a fabricated and ordered ensemble 0014 transmission of electrical power using light pho of a material as defined above; a source for exposing the tons; and ensemble to electromagnetic energy Sufficient to raise elec 0015 fabricating an accelerator on a chip, wherein the trons in the ring compound to an elevated level of excitement ordered ensemble comprises a large number of atomic and/or to Such a degree that a population inversion occurs, wherein molecular units aligned in Such a way that it can build up a the number of molecules in the excited States is greater than very high energy in the electrons transported down the chain the number of molecules in the lower energy states; and an in order to project a beam of electrons out of the end, thereby arrangement for contacting the fabricated ensemble with at creating a very tiny (micro) linear accelerator. least one chemical species that is capable of undergoing reac 0016. In other aspects of the invention, the method and/or tion in response to electron energy transferred from the ensemble.

device employs, as the molecular (and/or atomic) ensemble structure, a monolayer-type film of molecules deposited on a 0022. Further features of the invention will become appar Substrate, and in certain embodiments the film is deposited on ent from the detailed description of preferred embodiments Substrate having metallic conducting strips embedded at that follows, when considered together with the accompany intervals to collect electric currents. In other arrangements, ing figures of drawing.

the molecular (and/or atomic) ensemble structure is formed in BRIEF DESCRIPTION OF DRAWING FIGURES a three dimensional Volume.

0017. In other applications, the molecular (and/or atomic) 0023 FIG. 1 is a schematic diagram showing flow of elec ensemble structure comprises a plurality of molecular or trons in the Hill-Bendall model of photosynthesis. atomic species, at least Some of which function to bond to or 0024 FIG. 2 is a schematic representation of a photosyn at least interact with at least one chemical reactant. According thetic unit comprising a light-harvesting antenna and a reac to certain preferred aspects of the invention, the bonding tion center.

and/or interacting species comprise at least one metallic spe 0025 FIG. 3A shows the molecular structure of chloro C1GS. phyll.

0018. In certain preferred embodiments, the released 0026 FIG. 3B illustrates schematically chlorophyll mol energy from the stored energy also produces light, most pref ecules anchored to lipid layers.

erably coherent light. 0027 FIG. 4 is a schematic view of a pebble mosaic 0019. According to still other preferred aspects of the model.

invention, the method employs a length of exposure that is 0028 FIG. 5 is a diagram showing energy levels of elec Sufficient to produce multiple passes of a transferred electron trons on a closed ring of 20 atoms. thru the ensemble, whereby the energy in the electromagnetic 0029 FIG. 6 is a chart showing total binding energy of charge motion is increased with each pass, wherein prefer electrons on 20 atoms of the porphyrin ring in chlorophyll ably the active region of the atomic and/or molecular Versus the number of electrons on the ring. ensemble is terminated at each end of the region with a 0030 FIG. 7A is a chart showing the energy levels in structure suitable to reflect electrons (or holes) and reverse chlorophyll.

their motion, so as to cause oscillating transport of charges 0031 FIG. 7B is a chart showing the energy levels in an repeatedly passing through the pumped ensemble. ideal 4-level laser system.

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0032 FIG. 8 is a chart schematically showing three types 0054 Electrical Current Though Medium: of electron transitions. 0055 Passing a current through the P-N junction is 0033 FIG. 9 is a chart schematically showing triplet state employed to pump semiconductor lasers. Essentially most of formation by electron transfer in chlorophyll dimer. the electrons traversing the energy step at the junction can 0034 FIG. 10 is a schematic chart showing pumping of an produce an output photon. A similar process can be employed ensemble of molecules by electron transfer from the singlet for the present process, in which a current is passed through the molecular ensemble to excite electron states that can state to the triplet state of an adjacent molecule. produce energetic charge transport at right angles to the direc 0035 FIG. 11 is a schematic chart showing the decay of a tion of the stimulating current.

molecular ensemble by a stimulated emission of an electron 0056 Electron Beam:

polarization wave. 0057. Some lasers are pumped by direct impingment of 0036 FIG. 12A is a schematic cross-section showing energetic electronbeams Striking the active medium. It would chlorophyll molecules on the Surface of a non-polar solvent. be appropriate in the present process to employ electron 0037 FIG.12B is a schematic cross-section showing chlo beams striking the Surface of a film. rophyll molecules on the surface of a polar solvent. 0058 Gas Dynamic Process:

0038 FIG. 13 is a perspective illustration of semiconduc 0059 Gas dynamic or plasma dynamic processes can be tor device according to the present invention. used to pump gas lasers, but while this would not in most 0039 FIG. 14 is a schematic drawing of photovoltaic cases be directly applicable to an ordered molecular device using the EPWASER system. ensemble, the present process can employ a molecular 0040 FIG. 15 is a schematic illustration of a photochemi ensemble bombarded by gas stream, which can excite the cal decomposition system for converting water into hydrogen electron levels within the ensemble. and oxygen. 0060 Such input energy creates excited states of electrons 0041 FIG. 16A is a perspective view of a floating solar to produce a population inversion with the number of elec conversion plant for water decomposition. trons in excited States exceeding the number of electrons in 0042 FIG. 16B is a perspective view of the detail of the corresponding lower energy states. The excited electrons not photoactive surface in the system of FIG. 16A. only are raised to higher quantum energy level, but also trans 0043 FIG. 17A is a schematic plan view of a large scale fer to an adjacent molecule (or atom). The stored energy in floating photochemical plant. multiple molecules (and/or atoms) can then be released via a 0044 FIG. 17B is an enlarged view showing the detail of process very similar to stimulated emission, in which the the portion in the circle in FIG. 17A. excited electrons transition to a lower energy state while simultaneously jumping to an adjacent unit within the struc 004.5 FIGS. 18A, 18B and 18C illustrate three different ture.

ways of Subunit grouping in the porphyrin molecule. 0061. This action is similar to that of lasers, because the 0046 FIG. 19 is a graph of electron binding energy for an pumping process raises the energy states of electrons in a 18-atom ring molecule. number of atoms (and/or molecules); but, unlike lasers, the excited electrons are also transferred to a neighboring unit

DETAILED DESCRIPTION OF PREFERRED (atom or molecule). Once transferred, quantum mechanical EMBODIMENTS selection rules do not allow the electron to decay (de-excite) 0047. The present invention is directed to methods and back to its lower energy state within the same atom or mol apparatus to produce and to exploit a new physical process, ecule. In our process, the electronjumps to a neighboring unit which is similar to the operation of lasers, but different. Simi as part of its decay transition.

lar to laser operation, this process takes place in a special 0062 Lasers amplify light passing through the “pumped' group of molecules (and/or atoms), which can store input medium by a process known as stimulated emission. When a energy (pumping) that can be in the form of light photons, photon passes near a molecule or atom that has an excited or other forms of electromagnetic energy. Some of the pos electron, the oscillating electromagnetic field of the photon sible methods for pumping excitation energy include the fol “stimulates an excited electron to return its lower energy lowing: state, thereby giving up its energy and emitting another pho 0048 Light (Electromagnetic Radiation): ton, which has the same wavelength and is traveling the same 0049 Light (either pulsed or continuous) can be used as a direction in phase with the photon that stimulated the transi tion. Repeated events of this kind build up the intensity of the source of photons to excite electrons into excited states for the light within the laser; in a laser the light is “coherent because present process. The light source is not limited to the visible all of its photons are moving in the same direction, with the spectrum—it may be even be X-rays or infrared. same frequency, and in phase.

0050 Electrical Discharge: 0063. In our process, as an electron decays by jumping 0051 Electrical discharges are sometimes used as pump into the neighboring atom or molecule, it stimulates that ing sources for lasers. Either a diffuse discharge through the adjacent unit, which also contains an excited electron, to also gaseous medium, or an array of Small arc discharges can be decay and transfer its electron to the next unit down the line. used to excite electrons in the laser medium. A similar process This process can be continued down an arbitrarily long chain can be used for excitation of electrons the present process, of excited units, and it would thus sum up or combine the preferably in the form of an array of discharges impinging excitation energies of all the excited electrons by depositing upon a surface of a film of the molecular ensemble. that energy into the motion of the charges. The chain of units 0052 Chemical Reaction: does not have to be a long one; it could be as Small as two 0053 Excited electrons in compounds or radicals pro individual atoms or molecules. This process causes a coher duced by chemical reaction can be a source of energy input ent electric pulse to be directed along the axis of the structured for the present process. molecular ensemble. The electric pulse consists of a high

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energy electron moving in one direction, with a high-energy have many attractive features. Hydrogen and oxygen can be hole moving in the opposite direction. The electron energy stored indefinitely and converted to electric energy with high wave created can also be in a coherent form, and it can also efficiency (approximately 90%) in fuel cells. However, a pro include light emissions in some instances, such that it there cess which duplicates natural photosynthesis is even more fore has the same broad spectrum of applications as the emis attractive because it can provide organic chemicals including sions produced by a laser. food, and will generate no by-product pollutants during com 0064. Similarly to the case of the laser, the electron energy bustion.

wave created according to the present invention can be 0068. Several attempts have been made to use photoredox viewed as a stimulated emission. Stimulation can be sponta reactions (involving ferrous ions or ceric ions) for photolysis neous in accordance with the invention, meaning that certain of water. Other work has been directed toward multi-step of the excited electrons often begin to spontaneously decay decomposition of water. One investigation has attempted to back to their normal state in a statistical manner, as in the case modify the photosynthetic process in blue algae with dyes to of a laser, and this is a function of the amount of energy being accomplish hydrogen production. Potential efficiencies of pumped into the system. In other applications, it is appropri these various approaches are lower than photosynthesis. ate to apply some form of external stimulation to the systems, 0069. There is a lack of a feasible hypothesis to explain the in order to exercise control over the system. Any type of mechanism that occurs in plant photosynthesis. This mecha external stimulation can be employed, for example, electro nism allows a plant to collect and integrate the energy of 8 or magnetic energy or vibrational energy. When the charge level more low energy photons and utilize this energy in a single of an electron drops, it causes an oscillation which then stimu photochemical reaction to split water molecules. Quantum lates other electrons, at the appropriate frequency. mechanical considerations indicate that simultaneous action 0065. The process comprises an Electron Polarization of several photons of incoherent light is highly improbable. Wave Amplified by Stimulated Emission of Radiation (EP Photosynthesis must therefore involve the cooperative utili WASER) to create energetic charge movement, which has Zation of the energy of several photons. A method that dupli enough energy to drive chemical reactions that normally cates this cooperative photon action in vitro creates the pos would be impossible because the energy steps are larger than sibility of Successful large-scale photochemical energy, for the energy in a photon of visible light. In certain embodi example, in accordance with one embodiment of the inven ments, at the end of a series of the pumped units there is tion, the high efficiency solar decomposition of water. located a "docking site' interface that connects to a chemical 0070. In plant photosynthesis oxygen is not evolved from reactant, e.g., a water molecule, which can be split into hydro CO but rather from water with hydrogen utilized for storage gen and oxygen. The energy required to decompose water is of chemical energy by the buildup of carbohydrates. The larger than the photon energy (hv) of visible light; but our chemical balance of the carbon cycle is illustrated in FIG. 1. proposed process is capable of accomplishing this feat due to When the reaction shown at the top of FIG. 1 proceeds toward the novel mechanism described above. the right it represents the photosynthetic production of oxy 0066 An attractive approach to solar energy conversion is gen and /6th of a glucose molecule from water and CO. to directly utilize a process similar to photosynthesis which When the reaction proceeds toward the left, glucose is oxi occurs in plants. With respect to this field of utility, the ben dized (as occurs in animal metabolism). As indicated, efits of utilizing a photosynthesis-like conversion of Solar approximately 5 eV of energy are transferred by this process. energy to produce usable chemical fuels is widely recog A similar amount of energy is stored by splitting 2 molecules nized. However, the search for a suitable process is hampered of water to produce 2 molecules of free H and one of O. by a lack of fundamental knowledge regarding the basic (0071. The flow of electrons from water to carbon dioxide mechanisms of photosynthesis which allow the energy of proceeds against an electrochemical gradient of 1.2 volts and several incoherent photons to be cooperatively utilized to split requires two photochemical events. Four electrons must be water molecules. Our research has led to the discovery of a transferred, one at a time, to liberate a molecule of oxygen and novel mechanism to explain this efficient conversion of light reduce a molecule of carbon dioxide to carbohydrate. The energy. The process, which results in the formation of an process begins with the absorption of a photon by the antenna electron energy wave in aggregated molecular ensembles, as of pigment system II (PS II). The energy of excitation is discussed above, is now explained in more detail with refer conveyed to a chlorophyll molecule in the reaction center of ence to one non-limiting, exemplary type of molecule, the photosynthetic unit; the molecule is designated P680 namely, chlorophyll. A quantum mechanical model shows because one of the bands in its absorption spectrum is at 680 that in closely associated groups of molecules Such as those nanometers. The excited P680 transfers an electron to the comprising chlorophyll, light absorption can lead to electron acceptor Q, and Subsequently recovers an electron from the transfer between adjacent molecules. This type of inter-mo donor Z. After Zhas given up four electrons it regains them by lecular electron transfer will populate a metastable state such oxidizing two molecules of water. as the chlorophyll triplet state (normally spin forbidden in 0072 Experiments have shown that it is possible to make isolated molecules). Successive photon- or other energy-in the first photosystem (PS II) act to split water and evolve duced electron transfers will thus create a localized popula oxygen even though the second system (PSI) is inactive, thus tion inversion. In the stimulated emission process, electrons the possibility of utilizing the water-splitting part of the pro return to the ground state of an adjacent molecule. This occurs cess independently.

because the decay of the triplet state is spin-forbidden within 0073. As shown in FIG. 1 the difference in chemical bond a given molecule. energies of the reactants and the products of photosynthesis 0067 Examination of the photosynthetic process shows represents 5 eV of Gibbs free energy. The process of photo that the energy conversion efficiency can be as high as 34% at synthesis requires an input of two groups of 4 photons (8 the molecular level. Clearly a system which duplicates the total) and each photon must have an energy 1.85 eV (lowest water decomposition characteristics of photosynthesis would singlet excited State). If the energy of the incident light is just

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at this lower limit, the efficiency of photosynthesis is maxi not be transferred with energy available from a single photon mal. Thus the maximum efficiency of energy conversion is captured in the chlorophyll antenna. computed as 0079 Consider the process of creating the 4th electron hole pair. Since 0.8 eV is required to free the electron from its bound site in the absence of any neighboring charges an 5 additional amount of energy will be necessary to move the 5eV(8(1.85eV)) = 1 - 34% electron away against the electric field created by the 3 pre viously accumulated positive charges. This total energy is 0074 Since equal numbers of photons are involved in both represented as follows:

PS I and PS II, use of only the first (water splitting) step approximately cancels the loss incurred by averaging over the 2 1 1 1 (2) solar spectrum. Thus, the 34% conversion efficiency repre sents a potentially realizable efficiency.

0080 Where is-o I0081 e=the electron charge 0082 e-permitivity of the medium

OH-CH I0083 r, r, r the respective distances between site of the !------------- 4" hole, and each of the 3 previous charges.

I0084. A rough approximation of a numerical estimate of ------------ the energy can be calculated by assuming that the charges are

arranged in a square pattern as shown.

NOT TRUE

0075) Chemical Reactions of Photosynthesis 0076. The water-splitting step (PS II) requires 4 electrons to be transferred, one at a time, from the reaction center (indicated by Z and P680 in FIG. 1) by 4 separate photons.

During this process the electron donor associated with the reaction center acquires a positive charge which is neutralized when 2 molecules of HO are split. The existence of 4 sepa 0085. Then if L is Expressed in Angstrom Units: rate steps is demonstrated by experiments using a sequence of short intense pulses of light. It is found that oxygen produc tion is maximized in a third flash and is thereafter followed by 1 a damped cyclic variation with a period of 4 flashes. The existence of positive charges is Supported by electron spin

resonance work which indicates the presence of chlorophyll and ions in the photosynthetic unit during the photochemical act. 39

0077 Although not wishing to be bound by any particular theory, we believe that the photons are captured by a “light antenna' consisting of an array of closely associated chloro I0086 A conservative and reasonable assumption is that L phyll molecules. The energy of these photons is then trans is less than the intermolecular distance of chlorophyll mol ferred to the reaction center by a highly efficient process. ecules in the photosynthetic unit. The spacing of chlorophyll There is evidence that the excited state caused by light molecules must be on the order of ~10 A for efficient exciton absorption subsides to the first singlet state of chlorophyll transfer of energy between the “antenna' and the reaction before the energy can be transferred to the reaction center. center. IfL-10A, then the energy to remove the 4th electron Thus, the energy is delivered to the reaction center in units is ~4.7 eV. Clearly this energy step is so large that the 4th that are less than 1.85 eV (the energy of the first singlet). This electron could not be transferred with 1.85 eV photons. In value of 1.85 eV is considered to be adequate to raise an fact, trouble is encountered with all but the first electron electron from the reaction center to an acceptor energy level unless there is some mechanism in the photosynthetic unit that is located as high as 0.8 eV upward in redox potential. which can temporarily store the energy of several photons and 0078 However, if multiple charges are to be transferred, then simultaneously release all of the stored energy. only the first electron is transferred against a potential of 0.8 I0087 We believe that photosynthesis depends as much on eV. The energy to move the succeeding electrons will be the structural ordering and arrangement of molecules in the increasingly larger as the positive charge accumulates. If the photosynthetic unit as it does on the chemical constituents charges are located in close proximity (which presumably that are present. Most of the chlorophyll molecules function they must be, since they act together on separate molecules of as pigments to absorb light. Other pigments, such as the HO), the energy required to remove the last electrons will be carotenoids, that absorb strongly in parts of the spectrum significantly greater than 1.85 eV. Thus the electron would where chlorophyll does not absorb (such as yellows and

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greens) are also present and provide better usage of the Solar action with light involve the conjugated electrons in the por spectrum. We apply this principle to our invention, as well. phyrin head. There are no conjugated bonds in the phytyl tail. 0088. The arrangement of these photosynthetic molecules The Small groupings attached to the outside of the ring also is important in that they must act as a light antenna and then have little effect on the spectral properties. Hence, it is rea transfer the energy of photon absorption to a reaction center sonable to consider only the ring headina simplified model of shown schematically in FIG. 2. However, the light antenna the molecule.

pigments do not seem to participate directly in the electron 0096. Taking the view of the porphyrin ring as being a transfers or the chemical processes. segment of a one-dimensional atomic lattice which is joined 0089 Chlorophyll a is found in all photosynthetic organ into a closed loop, we can then make a quantum mechanical isms except bacteria. It has a molecular weight of 893.5 and calculation to obtain a relationship for the energy levels of the the structure shown in FIG. 3A. Several forms of chlorophyll electrons in the ring. Although this type of calculation is occur in vivo. The chlorophyll molecules have a flat circular approximate, we will later show that the result has some “head” (a porphyrin ring) approximately 15A by 15A in the additional generality.

center of which a magnesium atom is covalently bonded. 0097. The wave function for electrons in an infinite array Attached to the head is a phytyl “tail” approximately 20 A in of atoms with regular periodic spacing is a type of Bloch length containing 20 carbon atoms. The porphyrin ring is function and has the form of a plane wave modulated by a hydrophilic, and the phytyl chain is hydrophobic. The small function with a period equal to the lattice spacing. When the groupings attached to the outside of the ring have little effect infinite array of atoms is converted to finite length in a closed on the spectral properties. It is thought that the phytyl chain loop, an additional restriction is imposed on the wave func provides a nonpolar anchor to the lipid membranes insuring tion to exactly repeat itself after going all the way around the proper orientation relative to each other and the other com ring. The energy levels of an electron on Such a closed ring are ponents with which they interact. See FIG. 3B, which shows given by:

chlorophyll molecules anchored to lipid layers by their hydrophobic tails.

0090 Chlorophyll b is found in most plants and differs Ek = E0 - 2Acoska from chlorophylla only by having a formyl group in place of a methyl group on Ring II. It is not thought that chlorophyll b ka = 2nt

is essential to photosynthesis. The remaining forms of chlo rophyll occur in bacteria and differ from green plant chloro phylls in that they contain slightly different porphyrin rings. 0098. Where 0091 Photo systems I and II of higher plants appear to be (0099 E. energy of the kth level structurally distinct entities, each with approximately 250 0100 N-atoms in the ring light-harvesting chlorophylls and a special chlorophyll group 0101 a-lattice spacing acting as a reaction center. The two photosystems have been 0102 m integer separately isolated. Photosystem I contains chlorophyll a 0103 All possible energies are obtained by choosing: molecules, very little or no chlorophyll b and carotenoid 0104 -N/2>mN/2 pigments. The photosynthetic system known as Photosystem 0105. The values of E and Aare not obtained by this type II consists of chlorophyll a with approximately one-third of calculation. It is unimportant what value is taken for E chlorophyll b. since all energies are relative to arbitrary choice of the Zero 0092. The reaction center complexes are highly ordered level. The appropriate value of A can be obtained by compar molecular aggregates, and a relatively small number of chlo ing spectral data and heats of formation for various sizes of rophyll molecules in a specific arrangement are present as organic ring compounds. However, for our purposes in dis parts of the reaction centers. These chlorophylls are the cussing the energy levels of chlorophyll, only the relative molecular aggregates which use photon energy to accomplish spacing between levels is of concern, So it is sufficient to note electron transfers. that A is a positive constant.

0093. A conceptual picture of the photosynthetic unit is 0106. A convenient representation of the energy levels in shown in FIG. 4. This structure represents the pebble mosaic Eq. (5) is a circular diagram as shown in FIG. 5. The circle is model of photosynthetic lamellae. The reaction centers as divided into N (N=20 for the porphyrin ring) equal segments. well as the electron donors and acceptors are depicted sepa The vertical distances between points on the circle are pro rately from light absorbing molecules which make up the bulk portional to the cosine term in Eq. 5. The lowest energy level of the unit. is obtained with m=0 and E=E-2A. This energy level can 0094. In the pebble mosaic model, a series of repeating contain only two electrons with opposite spins by the Pauli units of the type shown in FIG. 4 are anchored to lipid mem Exclusion Principle. However, note that the other energy branes which form closed disc-shaped sacs. These thylakoid levels about m=0 each correspond to two values of m (i.e., discs are stacked like wafers in the chloroplasts. The orienta m t1, t2 . . . etc.), so the higher energy levels can each tion and arrangement of the chlorophyll molecules in the lipid contain up to four electrons without violating the exclusion membranes is not known exactly. However, it is believed that principle. As each level is filled, an “energy shell' is com at least some of the chlorophyll are very closely packed. pleted and the configuration is especially stable at those 0095. The outside of the porphyrin ring which forms the points. This is analogous to the atomic energy level structure hydrophilic head of the chlorophyll molecules can be thought in inert gases.

of as a closed-loop chain of 20 carbon atoms. Around the 0107 To find the ground state energy of the molecule, we outside ring are a series of alternating double-single bonds (II first consider the molecule with all electrons removed (i.e., 20 electrons) which can be excited by photon absorption. Virtu times positively ionized). The total binding energy is com ally all of the properties which relate to the electronic inter puted as the electrons are added filling the lowest level first,

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the second lowest next, and so on until all the electrons are has a flat bottom for the last four electrons. In other words, present. It is assumed that as the electrons are added to the rings of 4, 8, 12, 16 or 20... etc. units all have the property system that the energy levels are not changed by electron that two electrons can be added or removed without materi electron interactions. The total energy can be represented in a ally changing the binding energy. This permits the model to simple diagram using Eq. 5 with N=20 and E=0 (The value be applied to porphyrin rings or similar molecules of E is arbitrary as stated previously.) (N-multiple of 4).

0108 FIG. 6 is a plot of the total binding energy of the 20 0112 The porphyrin ring of the chlorophyll molecule is atom porphyrin ring versus the number of electrons in the made up of four sub-units which are pyrrole groups. Thus it is ring. The horizontal axis, which shows the number of elec possible to group the atoms which make up the porphyrin ring trons, runs from 0 to 40. At the midpoint of the curve, where in any of three possible arrangements shown in FIGS. 18A. there are 20 electrons (one for each atom), the molecule is 18B and 18C. In FIG. 18A the porphyrin ring is considered as neutral. At the beginning and end of the binding energy curve, a closed ring of carbon atoms, forming 20 units shown by the the molecule is 20 times positively ionized and 20 times dashed lines. In FIG. 18B, the ring is composed of 4 groups negatively ionized, respectively.

0109 Referring to Eq. 5 and the energy level diagram of with 4 connecting atoms, to form a total of 8 subunits. In FIG. 18C, the ring is composed of 4 subunits, again shown by the

FIG. 5 we will see how the binding energy curve as shown in dashed lines. All of these arrangements have four-fold sym FIG. 6 is built-up. The first two electrons go in at the m=0 metry. Consequently, no matter which arrangement is used to leveland each contributes an energy of -2A for a total of -4A. model the porphyrin ring, a flat bottomed binding energy Thus, we have the first point at two electrons and energy-4A curve of the type shown in FIG. 6 will result. Thus, the (The energy axis in FIG. 6 is plotted in arbitrary units of A). calculation that two electrons can be either added or removed The next four electrons go in at the m=1 level, and each from the porphyrin ring with only a small change in the contributes -2A cos (2/20)=1.9A. This gives the second point binding energy has considerable generality despite the fact it at six total electrons and total energy -11.6 A. This process was derived on the basis of a 20 atom ring. continues in segments of four electrons, each with decreasing slope in the energy curve, until we have reached 18 total 0113 Although chlorophyll a has 20 atoms in its outer electrons. The next level to be filled is at m=5, but cos 2(5) ring, only 18 of these atoms have alternating double-single JL/20=cos(L/2)=0. There is no appreciable change in the bind (conjugated) bonds. It is believed that the well-known Huck ing energy as we go from 18 to 22 electrons. Thus, the bottom el's rule (4N+2), which describes conditions for stable aro of the binding energy curve is flat. Furthermore, a closed matic ring compounds, applies to the 18 atoms (not 20) in energy shell occurs not with the neutral molecule, but with chlorophyll. This brings into question how many atoms two electrons either added or removed. should be used to estimate the energy levels for electrons with 0110. The consequence of the flat bottom on the binding a periodic wavefunction on the chlorophyll ring should the energy curve is that a porphyrin ring can gain or lose two number be 20 or should it 18, which is a 4N+2 number. The electrons with a negligible change in the total binding energy. operation of the EPWASER process does not depend on the Furthermore, it would tend to do so to improve its stability by number of atoms in ring molecule. The only thing of impor closing the energy shell. With two molecules next to each tance is that the binding energy is such that an excited electron other, additional stability is obtained by two electrons moving can easily transfer from one molecule to the neighbor. from one molecule to its neighbor. This will create a closed 0114. In the treatment of the previous pages it was shell in both molecules, (one positively ionized and one nega assumed that the Schrödinger wave function only makes a tively ionized, but with the overall pair being neutral.) The single loop around the ring and then reconnects with matched EPWASER mechanism employs the concept of pumping by phase. However, other pathways are possible. This is particu transfer of electrons between molecules without significantly larly relevant when there is group of closely packed rings, changing their energy levels, and we use chlorophyll here as Such that the wave function of one ring might interact with one example of Such a molecule. By applying this same neighboring molecule(s). In fact the combination of mol methodology, it is routine to identify other Suitable com ecules in a dimer (or larger ensemble), may be regarded as pounds that exhibit this type of behavior with respect to their something like one “super molecule' energy level properties. Software is commercially available that enables calculation of quantum energy levels for any 0.115. In addition to single loop orbital paths, there can compound. also be loops as proposed by Clapp to describe the spectrum 0111. The simplistic model (20 atom ring) which was used of Chlorophyll Clapp, Roger E.: “Loop Currents in Chloro to develop the binding energy relationship given by Eq. 5 and phyll-a’: Basic Research Associates, Incorporated, Cam FIG. 6 is a very approximate representation of the actual bridge, Mass. 02138, USA: Theoret. Chim. Acta (Berl.) 61, molecule, because of porphyrin ring contains other atoms 105-133 (1982). For a Mobius loop, the wavefunction makes besides the 20 carbon atoms. However, we shall now show a “twist' which creates a phase shift equal to one half wave that the result of the calculation for chlorophyll has additional length as it goes around one time. The path completes the generality. The derivation of Eq. 5 depends only on the sym phase change to match the beginning point after 2 circulations metry properties of the system. Nothing is assumed regarding and reconnects. This type of behavior would be more likely to the type of potential which binds the electrons to the atoms. occur with closely stacked molecules having rings adjacent to Instead of a ring of atoms, a ring of any other subunits would each other. It is possible to apply the same type Bloch wave be adequate. The Subunits are ideally identical and regularly function calculation to a Möbius loop, and estimate the bind spaced around the ring. As long as this condition is met, the ing energy. In that case the phase shift would be an odd result obtained in Eq. 5 remains valid. It can be verified that as numbered (2m+1) multiple of TL. There is a similar equation long as the number of units which make up the ring (the value for the energy levels with odd multiples of L: of N in Eq. 5) is a multiple of four, the binding energy curve

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0116. Where m is an integer and N is the number of atoms order to obtain lasing action, an excited State with a long in the ring lifetime is required. This state is populated far above the 0117 Applying this equation to calculate the binding equilibrium level. The resulting de-excitation of this level energy curve for an 18 atom ring with a Mobius pathway through stimulated emission produces the lasing action. gives a curve with flat bottom binding energy as shown in However, the requirement of a long lifetime (a forbidden FIG. 19 of the drawings. transition) also implies a very Small cross-section for adsorp 0118 FIG. 19 shows the calculated relative binding tion of light. Thus, it is seldom possible to directly pump the energy (arbitrary units plotted positive) for an 18 atom ring level which is involved in the lasing process. As a result, an with 2 cases: one with single loop pathway (dashed line with indirect pumping scheme is most often used. diamond data points) and also for Mobius loop (solid line 0.124 First, some level slightly above the lasing level is with circles marking data points). Looking at the Mobius pumped by light absorption or some other means of energy curve there is no change in the binding energy from 16 input (see FIG. 7B). A radiationless transition (e.g., colli through 20 electrons. In other words, the molecule could gain sional) is used to transfer this excitation to the metastable or lose electrons without gaining or losing energy, which is level which becomes overpopulated. In this way the problem important. This means that the question about considering of a low adsorption cross section implied by a long lifetime is chlorophyll with 18 atoms instead of 20 is resolved. It also avoided.

means the other candidate molecules having varying numbers 0.125 Stimulated emission occurs when a photon passes in of carbon atoms in the ring, e.g., following the rule of 4N--2, the near vicinity of an excited atom. If the energy of the are useful for EPWASER media, such as a ring containing 18 photon matches the excited atom level, the oscillating electric atoms, as discussed above. The molecule coronene, which field of the photon can stimulate the excited atom to decay by has 18 atoms in its outer ring is such a candidate that we have emitting a second photon. Unlike ordinary light (spontaneous tested. emission) this second photon is emitted in the same direction 0119 Coronene solution was deposited very slowly in and in phase with the first photon. Thus the oscillating electric Small droplets onto a glass slide. Evaporation was controlled fields of a group of photons produced by Stimulated emission so that the material had an opportunity to form Small crystals are vectorially additive. Very large transient electric fields can of coronene on the slide Surface as the solvent evaporated. be produced in this way, as has been demonstrated with lasers. When this ensemble was irradiated with 405 nm laser exci 0.126 The coherent electric field explains generally how tation source, it produced bright emission, which was a spec an electron can be removed from a donor which has previ trally very narrow line in the green range of the spectrum. This ously accumulated a positive charge. More specifically, how type of response was only seen with crystalline coronene-a ever, an electron is transported by a process slightly different very different, broader spectrum, fluorescence was observed from stimulated emission of radiation. This process involves from coronene in a solution of hexane. Line narrowing and stimulated emission to produce an electron polarization brightness amplification are characteristics which indicate wave. We will now explain how this occurs. output produced by stimulated emission. Light output driven I0127. To begin the description it is helpful to consider by stimulated emission is considered to be evidence of opera explicitly the difference between ground state, excited singlet tion according to the invention. state, and metastable triplet state as shown Schematically in 0120 A diagram of the energy levels which can be excited FIG.8. Inspection of the figure shows why it is difficult for an by light absorption in chlorophyll is shown in FIG. 7A. The electron to achieve the required spin alignment to enter the lowest absorption band represents the singlet state located metastable triplet state. Mechanisms that can change the spin approximately 1.85 eV above the ground state. Absorption in are magnetic fields, and collisions, which are not present in any higher singlet States decays into the first singlet state by the system. The situation shown in FIG. 8 represents an iso internal conversion before the excitation is lost or transferred. lated molecule. However, the situation is somewhat different There is also a metastable triplet state which is located if we consider more than one molecule in close proximity. In slightly below the first singlet. the previous discussion of the binding energy of electrons in 0121 The triplet state has an extremely long lifetime suitable molecular structures as described earlier herein, we because the transition back to the ground state is forbidden by have shown that an electron can be transferred with very little spin prohibitions. Conversion between singlet States and trip change in the total energy. Thus, if a neighboring molecule is let states is possible and known. However, this is unlikely close enough that the wavefunction of the excited electron in because a reversal of the electron's spin is required. In the a singlet state overlaps the second molecule, excited electron current concept in the literature of photosynthetic processes, transfer to the adjacent molecule can take place. the role played by the triplet state is believed to be small. The 0128. As an example, consider a dimer, two closely asso main reason for the de-emphasis of the triplet state is the fact ciated molecules, A and B, as illustrated in FIG. 9. Assume that it has a low probability for excitation by light absorption that a photon is absorbed in molecule A creating an excited or Subsequent interSystem crossing. As mentioned earlier, singlet, and the excited electron Subsequently transfers to light absorbed in the chlorophyll molecules of the “light molecule B. Molecule A is now positively ionized and mol antenna' is believed to be transferred to the reaction center ecule B has one extra electron. Suppose a second photon is only as a singlet state excitation. now absorbed in molecule B, exciting one of the ground State 0122. A mechanism is described here that allows the electrons into a singlet state, and this electron transfers back energy of several incoherent photons to be stored in aggre to molecule A. The result now is that we have two molecules gates of molecular or atomic structures, which are composed each with spin-aligned electrons in excited triplet states. of atoms or molecules with energy levels as described earlier I0129. This type of process is not limited to two molecules. (FIG. 6) and then released preferably coherently. A group of any number of molecules can also be pumped into (0123. Before beginning the discussion of EPWASER, the the triplet state if they were all ordered in close proximity. A characteristics of stimulated emission are briefly reviewed. In schematic of how this can occur is shown in FIG. 10. There

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are several criteria that will determine how long the stack of charge imbalance can be sufficient to initiate a decay process. structures will be, including the breakdown voltage of the This type of decay implies that the decay begins along the end media that encapsulates the stack, how large a Voltage field of the stack. The ends of the molecular stacks are typically the structure can withstand, and how efficient the excitation terminated in electron donors or acceptors; however, the system is. Ultimately, the length of the stacks depends on the donors/receptors need not be located at the ends, but rather amount of energy needed for any particular utility. For a can be interspersed throughout the Stacks. In some cases, the chemical reaction, such as water splitting, a stack length of presence of impurities can perform the same function as the about 2 units will Suffice; however, for an application Such as donor/receptor, i.e., prompting discharge. photovoltaic energy conversion, a stack length Sufficient to I0136. The termination of the EPWASER decay process generate a voltage of several 10's of volts is needed. Each unit typically also occurs at one end of the molecular stack which in a stack generally contributes from about 0.5 to 1 volt. makes up the ensemble. A final result of the release of stored 0130. In FIG. 10 we see that each molecule in a linear array energy by the stimulated emission mechanism is to produce which makes up an ensemble donates one electron to its either an energetic electron or a positively charged hole. The neighbor by the same process as described for the two energetic electron can be one which is moved from a posi coupled molecules. The electron which is transferred is first tively charged donor requiring a large energy step as dis excited to the singlet state by light absorption and produces a cussed earlier. An alternative is that the energy is utilized by triplet only after being transferred to the adjacent molecules. the positively charged hole to interact in a separate chemical One photon per molecule is necessary to excite the entire process, Such as the removal of an electron from a water ensemble into the triplet state. After each molecule is excited molecule. The energy accumulated by the hole during the to the triplet state the electron spins are aligned in each mol decay process can be applied to overcome the energy barrier ecule, but the direction of the spins alternate between adjacent to remove an electron from water.

molecules. I0137 The first step in synthesizing an EPWASER device 0131 Referring once again to FIG. 10, the spins of adja is a method of creating an ordered array of the selected mol cent molecules are alternating. Thus, decay of an excited ecules, for example, chlorophyll. One method of accomplish electron between adjacent molecules is spin-allowed, while ing this is to float the molecules, e.g., chlorophyll, in a Surface decay within a particular molecule is spin-forbidden. Conse monolayer on a non-polar liquid. An illustration of this is quently, the decay of the ensemble occurs when an electron given in FIG. 12A. The hydrophobic tails 30 will be attracted goes from the excited triplet state of a given molecule to the to the polar liquid 32 and hydrophilic porphyrin heads 34 of ground state of an adjacent molecule. This produces an oscil the molecules will remain on the surface, with hydrophilic lating electric field which in turn stimulates the next molecule heads pointing upward and the tails pointing downward. The within the line to decay in a similar fashion. upper image shows the dissociated chlorophyll molecules 36 0132 An illustration of how this can occur is shown in on the surface of the polar solvent. FIG. 11. The following sequence of events occurs. Some 0.138 If this surface monolayer is now cooled (and com where within the group, perhaps starting at one end of the pressed if necessary), the chlorophyll molecules will tend to stack, an electron in the excited triplet state goes to the ground form associated aggregates undergoing a process similar to state by crossing over to the adjacent molecule. At the same condensation in two dimensions. The formation of these mol time it generates an oscillating electric field with the proper ecule aggregates will cause the porphyrin heads of the chlo frequency to stimulate that molecule to also decay. Since rophyll molecules to link to closely associated linear stacks in there are now three electrons in the molecule it has a very high the chloroplast structure. The number of molecules in each probability for decay into an adjacent molecule causing the aggregate will be variable and will depend on the degree of next down the line to do likewise, and so on. The result is that nucleation of the two dimensional crystals. one electron is transferred down the entire stack in a series of 0.139. By dipping a microscope slide into the solution it is sequential steps. At each step the energy stored in the triplet possible to remove the molecular film intact from the surface. state is given up and added to the oscillation which moves Depending upon whether the microscope slides are coated down the line. The particle which travels here is not a photon with a polar or non-polar material, it is possible to cover the but rather an electron polarization wave. slide with many layers of the molecular film by successive 0133. The quantum mechanical description of the moving dippings or to have only one covering regardless of the num particle is more like a polaron than a photon. The distinguish ber of dippings.

ing feature between the two types of particles is that the 0140. Another method of preparing the chlorophyll polaron contains a charge as well as an oscillating field. molecular film is to use a polar liquid 40 such as water which Unlike stimulated emission of photons, the EPWASER decay orients the hydrophilic heads 42 down and the tails 44 up. An process takes place along the axis of the molecular stack in example of this is drawn schematically in FIG.12B. This type order for the quantum efficiency in the process to be high. of film with dissociated molecules 46 could also be con This decay process may also be thought of as generating a densed into molecular aggregates in which closely associated positively charged hole which moves in the opposite direction chlorophyll molecules 48 are produced, as shown in the lower down the stack. image.

0134. The initiation and termination of the stimulated 01.41 Each of these methods has its own advantages. The emission process should now be considered. The initiation of first method has some advantages in getting porphyrin heads the decay in a molecular ensemble can start at any point where more closely associated than the tails. On the other hand, the an asymmetry occurs. This can involve either end of the stack. second method seems to more clearly simulate the natural 0135 Another event which can trigger the release of evolutionary process which may have taken place to form the energy stored in the stack is the donation or acceptance of an primitive ancestors of early plants. Both methods of prepara electron, e.g., to remove one electron from, or add one elec tion, as well as various dipping procedures, are possible. For tron to, the molecule on the end of the stack. The resulting general guidance on carrying out the generation of these types

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of films, we incorporate by reference, each in its entirety, the These compounds have been used in Supramolecular elec following: I. a. S. V. Langmuir, J. Amer: Chem. Soc., vol. 59, tronics. They are known to self-assemble into a columnar p. 2075, 1937. phase. One derivative in particular forms carbon nanotubes, 0142. Other methods of fabricating the ordered ensembles and the columnar phase in this compound further organizes according to the invention can be employed to produce itself into sheets, which ultimately roll up like a carpet to form ensembles from varied types of materials and in various multi-walled nanotubes with an outer diameter of 20 nanom forms. For example, it is possible to fabricate a device accord eters and a wall thickness of 3 nanometers. The nanotubes ing to the invention by employing solid state fabrication tech have sufficient length to fit between two platinum nanogap niques. An embodiment of this type is described more fully electrodes produced by Scanning probe nanofabrication and below. In addition, it is also possible to employ nano-fabri are 180 nanometer apart.

cation techniques in order to construct an ordered ensemble 0146 In addition to chlorophyll-like rings of carbonatoms according to the invention.

0143. The special features of electronic binding energy with a count that can be evenly divided by 4 and coronene and levels which have been described herein have been ascribed similar rings that behave as a ring of six linked entities that to the porphyrin ring rather than to chlorophyll itself. Thus, can be excited into higher energy states, it is possible to other compounds with similar porphyrin ring structures or employ other compounds. Such as, ruthenium tris bipyridine. other structures that satisfy the relationships described above 0147 According to another embodiment of the invention, are also capable of EPWASER action. There are likely many a semiconductor diode is provided that is similar to a semi systems of conjugated bonds in molecules, preferably planar conductor laser diode, but instead of a laser, it uses the ring systems but not necessarily planar nor necessarily ring EPWASER system in order to produce an output in the form compounds, which possess the unique set of properties of an energetic charge motion. A device of this type is illus described above. trated in FIG. 13. The device comprises a p-type layer 10 and 014.4 For example, another ring compound that can be n-type layer 12, having an active layer 14 Sandwiched in used according to the invention is coronene. between. A heat sink layer 16 serves as a base, and an elec trical lead 18 is fixed to metal contact layer 20, formed on silicon dioxide layer 22. At the polished end 24, an output 26 in the form of an energetic charge motion is produced. A low

Voltage electric current passes through the semiconductor junction region (vertical direction in the illustration), where electrons from the N-region recombine with holes from the

P-region. The energy of recombination pumps the ordered ensemble of material to create a population inversion. The pumped energy is released by Stimulated transitions produc ing energetic charge motion along the axes of the molecular ensemble in a direction at right angle to the pumping current

Coronene (also known as Superbenzene) is a polycyclic aro (horizontal in the figure). This energetic charge motion is matic hydrocarbon (PAH) comprising six peri-fused benzene output from the end face of the device. A device of this type rings. Its chemical formula is C4H2. This aromatic com can be produced either by Sandwiching a layer of an ordered pound can be described by 20 resonance structures or by a set ensemble of EPWASER organic material, as described above, of three mobile Clar sextets. In the Clar sextet case, the most or by epitaxially growing the layers of the device employing stable structure for coronene has only the three isolated outer an inorganic EPWASER material having the properties sextets as fully aromatic although Superaromaticity would described above.

still be possible when these sextets are able to migrate into the 0.148. The mechanism of stimulated emission from the next ring. triplet State provides a means of storing the energy of 0145 Another suitable compound is one selected from the four or more quanta and utilizing it simultaneously. family of compounds known as hexa-benzopericoronenes, 0149 EPWASER energy storage by electron transfer is which are members of the coronene family. consistent with quantum mechanical predictions of the binding energies of the electrons in chlorophyll mol ecules.

0.150 Stimulated emission produces a large amplitude coherent electric field which contains the energy of mul tiple photons and may be employed in photochemistry, e.g., field ionization of water molecules.

0151. The EPWASER process can involve as few as two molecules (a dimer) or an associated ensemble contain ing any number of molecules.

0152 The release of the energy of the EPWASER mechanism produces an energetic electron-hole pair which is either involved in direct oxidation of another compound (e.g., water) or participates in transfer of charge from an electropositive donor.

0153. Many applications are possible using the stimulated emission and EPWASER mechanisms, particularly in the field of energy conversion. Some of the preferred applications are now described, including an EPWASER photovoltaic

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device and the EPWASER photochemical decomposition of process. This layer of molecular ensembles is the EPWASER water to generate hydrogen and oxygen for use in a fuel cell. medium which transfers electrons from the water to the con Other preferred applications are based on the similarities of ducting substrate 54. The outside of the metal substrate must achieving a lasing-like action with the EPWASER system, be insulated so that electron flow from the substrate is con e.g., with chlorophyll and other preferred compounds. In ducted up a wire 56 which is also insulated. The other end of other words, the EPWASER system is applicable to virtually the wire is connected to an insulated electrode 58 on the other all of the uses for which lasers are used. side of the galvanic cell which is in the dark. 0154) One preferred application comprises a photovoltaic 0.161 The two halves of the cell are separated by a mem device consisting of molecular aggregates formed from chlo brane 59 which is permeable to H+ ions. The H+ ions pro rophyll films. duced on the light side drift through the membrane and com 0155 Since the electrons and holes which are produced by bine with electrons on the other side to produce hydrogen gas. the EPWASER process have large energies they can be made In this way oxygen is evolved on one side of the cell and to climb the potential barrier and a type of photovoltaic cell hydrogen on the other side.

can be created using this mechanism. The energy of the 0162 Large scale photochemical conversion of solar charge carriers produced by the EPWASER depend on the energy can be accomplished in one embodiment as follows, number of molecules which are aligned in the linear stacks of with reference to FIGS. 16A and 16B. Flexible structures are the molecular ensembles. This in turn determines the voltage fabricated which are photochemical converters, as described of the photovoltaic device. Electrons from an EPWASER above, and these membranes are then floated over the surface whose molecular aggregates consist of dimers would be of a body of water 60. The photoactive part of the structure 62 capable of passing current over a potential barrier which is would cover a large area in order to intercept a large amount equivalent to the energy of two light quanta (~2x1.8 eV). of solar energy and is mounted on a conducting Substrate 66, 0156. If the molecular ensemble consists of linear stacks which is otherwise covered by insulating layers 68. The cov with a larger number of molecules, the energy of the charge ering 64 of the photoactive surface must also be transparent to carriers is proportionally increased. There is a practical limit light or have areas which are open for light passage. One side to the size of this Voltage because, at high Voltages, break of the photoactive surface must be in contact with the water. down within the film or leakage currents will neutralize the 0163. It is also necessary to have some means to collect the output power. In air, the limit is about 1.5 mm between con hydrogen and oxygen which are produced. The oxygen is ducting paths to remove the power. In pure water it is much evolved as a gas above the photoactive surface and is col larger, and in water with some salts, the limit must be deter lected in a flexible transparent cover 64 which inflates as the mined in-situ. The limits in impure water depend on the level gas builds up. The gas collection system has at least two of salinity in the water. In a controlled non-aqueous environ compartments to separate the hydrogen and the oxygen. The ment, e.g., a vacuum, Voltage breakdown limits go up to hydrogen collector compartments 69 are preferably opaque to approximately 10 or 10 volts/cm. light. A drawing of this type of apparatus is shown in FIGS. O157 To construct such a device there are first created the 16A and 16B.

associated molecular ensembles and then they are arranged a 0164. Electrons are separated from water by the conducting Substrate which contacts the terminations of the EPWASER process in the photoactive layers of chlorophyll linear stacks of the molecular arrays. A schematic of this aggregates. Oxygen is liberated at these Surfaces and col arrangement is shown in FIG. 14. lected under the flexible transparent covering 64. The elec 0158. Successful achievement of EPWASER action is part trons are collected by the substrate under the photoactive of the process to accomplish water-splitting for production of Surface and conducted to exposed hydrogen electrodes in the fuel from Sunlight. Operation of stimulated emission in adjacent compartments. Protons from decomposed H20 flow molecular aggregates provides the ability to collect and apply through the permeable membranes 72 which separate the the light energy to move electric charges. compartments to combine with electrons at the hydrogen 0159. In order to dissociate the water, H0 molecules must electrodes 74. This produces hydrogen gas which is collected be in contact with one end of the molecular stack and an in a compartment 69 with an opaque covering. The sloping electron transfer mechanism must be at the other end. In a sides 70 of the cover of the hydrogen compartment 69 are preferred arrangement, a chemical structure containing a preferably “mirrored to provide better light utilization. transition metal, preferably, manganese is utilized to provide 0.165. The structure is articulated at each joint between a contact with H20, i.e., an intermediary between the stack compartments. The proper water level is maintained by con and the chemical reactant(s). Most preferably, the transition trolling the amount of ballast in tubes 76 which are at bottoms metal is in the form of a manganese ions that also serve to of the permeable membranes 72. The oxygen collecting vol complex with the water and to stabilize the reactive interme umes are covered by the transparent films which are closed at diates S the water is split. However, the preferred manganese one end and connected to piping manifolds at the opposite complex is generally not necessary since a molecular aggre end. A similar type of manifolding arrangement gathers the gate of chlorophyll can directly remove electrons from water. hydrogen which is produced.

The use of a transitional metal in the contact site is entirely 0166 Multiple units of this type can be spread over the optional, as natural contact sites typically exist in the Surface of the water to convert Solar energy on a large scale. A ensemble structures themselves. layout of a large scale photochemical plant is shown in FIGS. 0160 Providing electron transport from the other end of a 17A and 17B, which is a detailed view of the portion circled linear stack which makes up the molecular aggregate can be in FIG. 17A. The plant is shown with separate hydrogen accomplished in one embodiment by connection to an elec storage vessel 80 and oxygen storage vessel 82, as well as trical circuit in a "galvanic cell 50 as depicted in FIG. 15. The separate hydrogen pipes 84 and oxygen pipes 86. process occurs as follows. Light acts on a layer of associated 0.167 A relatively large area must be covered to provide chlorophyll aggregates 52 to produce the stimulated emission power for a significant size installation. An estimate of the

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required area can be obtained as follows. A typical size elec its stored energy by producing a modulated transport through tric powerplant (1000 MWe) requires an input of 3000 MWe the chain of selectively pumped and de-excited units: at ~30% efficiency. This in turn requires a photoactive area of 0177 transmission of electrical power using light pho 3x10 m exposed to solar flux. Furthermore, this is adequate tons; and only at peak Solar flux. For base load operation, averaging the 0.178 to make an accelerator on a chip, wherein the insolation over day and night and the seasons approximately ordered ensemble comprises a large number of atomic or increases the amount of required area by a factor of 4 to molecular units are aligned in Such a way that it can build up 12x10 m (e.g., a 3 kmx4 km rectangle). a very high energy in the electrons transported down the chain 0168 This large area requirement gives strong motivation in order to project a beam of electrons out of the end, thereby to consider systems which are floating over a large body of creating a very tiny linear accelerator. water Such as the ocean. Such an off-shore plant is more 1. An energy conversion device, comprising: practical than consuming usable land area on the earth's a fabricated and ordered ensemble of a material comprised Surface. Since the products of a photochemical plant are of atoms and/or molecules that can store input energy in hydrogen and oxygen which are both storable and shipable, the form of electrons elevated to an increased level of the advantages of a land-based system seem to be rather excitement, wherein the ordered ensemble of material Small. In fact, a photochemical plant located at sea has attrac exhibits, between adjacent atoms or molecules, a rela tive features which would not be available with an off-shore tive binding energy for an excited electron that is suffi electric plant, because the electric plant requires a costly cient to render the material capable of a spin-allowed transmission line back to the shore. transfer of an excited electron to an adjacent atom or 0169. In addition to the production of hydrogen and oxy molecule in the ensemble to form a meta-stable configu gen, stimulated emission photochemistry has many other ration in which the excited electron is spin-forbidden to applications. Any endergonic chemical reaction which is dif lose its energy within the atom or molecule to which it ficult to accomplish because it requires a large energy step is has moved, and wherein the ordered ensemble of mate a candidate-for the stimulated emission process. The rial is likewise capable of releasing stored energy by EPWASER mechanism allows an aggregate of any number of means of a charge transfer between adjacent atoms or molecules to add photon quanta and build up very energetic molecules from an excited electron state to a lower state charge carriers. Thus, chemical reactions which require redox in the adjacent atom or molecule, in a manner that sums potentials of many Volts are possible. These chemical reac up a plurality of individual excitations in an output for tions can be used for the production of special materials the device.

requiring large redox potentials at low temperature for for 2. A device as claimed in claim 1, wherein the ordered mation. Other possible uses are information storage, imaging, ensemble of atoms/molecules comprises a ring compound or new types of photography. displaying a Sufficiently low binding energy to enable elec 0170 As mentioned before, many other organic ring com tron transfer to an adjacent atom/molecule in the ensemble. pounds, with conjugated double bonds in the ring (any ring of 3. A device as claimed in claim 2, wherein the ensemble 4, 8, 12, 16, 20, etc. atomic sites) can be used as an EPWASER structure comprises a monolayer-type film of molecules medium. The complete list of applications for a Successful deposited on a substrate.

EPWASER process is expected to be as large as have been 4. (canceled) developed for lasers. 5. (canceled) 0171 Preferred applications of the present device and/or 6. (canceled) process comprise: 7. A method of enhancing the intensity of electromagnetic 0172 applying the energy release to a chemical reaction, energy, comprising:

more preferably a reaction comprising splitting water mol exposing to a source of electromagnetic energy, a fabri ecules into hydrogen and oxygen. In this and other preferred cated and ordered ensemble of a material as defined in aspects of the invention, the application of the energy release claim 1, wherein the source of electromagnetic energy is is preferably to a photochemical process, which requires Sufficient to raise electrons in the compound to an energy steps greater than the energy contained in one photon elevated level of excitement to such a degree that a of light; population inversion occurs, wherein the number of 0173 conversion of photovoltaic energy; molecules in the excited States is greater than the number 0.174 applying currents caused by charge transfer for of molecules in the lower energy states; and modulating signals in circuits employed for communication, releasing stored energy by means of a charge transfer wherein the communication circuits comprise an optical between adjacent atoms or molecules from an excited fiber, an electric conductor, or a radio transmission system; electron state to a lower state in the adjacent atom or 0175 utilizing the released energy stimulated from the molecule, in a manner that Sums up a plurality of indi stored energy to imprint a pattern to store information con vidual excitations in an output. tent; 8. A method as claimed in claim 7, wherein the ordered 0176 storing the information is stored directly in the ensemble comprises an ordered structure of atoms or mol excited energy states of the atomic or molecular units of the ecules arranged close together so that the quantum mechani ensemble, whereby some selected units in a chain are pumped cal probability of location for excited electrons in a given unit to store excited electrons, while other selected units remain in overlaps into the location of adjacent neighboring units. their lower energy states in Such a way that the pattern of 9. A method as claimed in claim 7, further comprising excited vs. de-excited units becomes a form of encoded infor applying the energy release to a chemical reaction. mation. A method of retrieving the encoded information from 10. A method as claimed in claim 9, wherein the chemical Such a device comprises reading the variations of current that reaction comprises would be produced when the information ensemble releases splitting water molecules into hydrogen and oxygen.

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11. A method as claimed in claim 7, further comprising a source for exposing the ensemble to electromagnetic applying the energy release to a photochemical process, energy sufficient to raise electrons in the ring compound which requires energy steps greater than the energy contained to an elevated level of excitement to Such a degree that a in one photon of light. population inversion occurs, wherein the number of 12. A method as claimed in claim 7, wherein the ordered molecules in the excited States is greater than the number ensemble of molecules comprises chlorophyll. of molecules in the lower energy states; and 13. (canceled) an arrangement for contacting the fabricated ensemble 14. A method as claimed in claim 7, wherein the process with at least one chemical species that is capable of comprises conversion of photovoltaic energy. undergoing reaction in response to electron energy 15. A method as claimed in claim 7, further comprising transferred from the ensemble.

applying currents caused by charge transfer for modulating 30. Apparatus for electron energy amplification, compris signals in circuits employed for communication. ing:

16. (canceled) a bounded Volume containing a fabricated and ordered 17. A method as claimed in claim 7, wherein the ensemble ensemble of a material comprised of atoms and/or mol structure comprises a monolayer-type film of molecules ecules that can store input energy in the form of electrons deposited on a Substrate. elevated to an increased level of excitement, wherein the 18. (canceled) ordered ensemble of material exhibits, between adjacent 19. A method as claimed in claim 9, wherein the ensemble atoms or molecules, a relative binding energy for an structure comprises a plurality of molecular or atomic spe excited electron that is sufficient to render the material cies, at least Some of which function to bond to at least one capable of a spin-allowed transfer of an excited electron chemical reactant. to an adjacent atom or molecule in the ensemble to form 20. (canceled) a meta-stable configuration in which the excited electron 21. A method as claimed in claim 7, wherein the released is spin-forbidden to lose its energy within the atom or energy from the stored energy produces light. molecule to which it has moved, and wherein the 22. (canceled) ordered ensemble of material is likewise capable of 23. (canceled) releasing stored energy by means of a charge transfer 24. (canceled) between adjacent atoms or molecules from an excited 25. (canceled) electron state to a lower state in the adjacent atom or 26. A method as claimed in claim 7, wherein the length of molecule, in a manner that Sums up a plurality of indi the exposure is sufficient to produce multiple passes of trans vidual excitations in an output for the device, and ferred electrons thru the ensemble, whereby the energy in the wherein the ordered ensemble of material is likewise electromagnetic charge motion is increased with each pass. capable of releasing Stored energy by means of a charge 27. A method as claimed in claim 26, wherein the active transfer between adjacent atoms or molecules from an region of the atomic or molecular ensemble is terminated at excited electron state to a lower state in the adjacent each end of the region with a structure suitable to reflect atom or molecule, in a manner that Sums up a plurality of electrons (or holes) and reverse their motion, so as to cause individual excitations in an output for the device; and oscillating transport of charges repeatedly passing through an energy source which emits energy in a range which can the pumped ensemble. be absorbed by said ordered ensemble, the majorportion 28. A method as claimed in claim 7, wherein the ordered of the energy absorbed by said ordered ensemble caus ensemble comprises a large number of atomic or molecular ing transitions of the atoms or molecules thereof to be units aligned in Such a way that it can build up a very high elevated to said increased level of excitement, said energy in the electrons transported down the chain in order to energy source being arranged to direct energy into said project a beam of electrons out of the end, thereby creating a ordered ensemble to excite said atoms or molecules to miniaturized linear accelerator. emit electrons in the bounded volume when stimulated 29. An apparatus for carrying out a chemical reaction, to do so by the presence of stimulating energy due to comprising: transitions from the elevated state to a lower state in an a fabricated and ordered ensemble of a material as defined adjacent atom or molecule.

in claim 1: k k k k k