VIBRONIC INTERACTIONS OF WATER CLUSTERS AND USES THEREFOR

[0001] This application claims priority to U.S. Provisional Patent Application Ser. No. 60/978,836, filed on October 10, 2007, entitled "Vibronic Interactions of Water Clusters and Uses Therefor", which is incorporated herein in its entirety by reference.

FIELD OF THE DISCLOSURE

[0002] The present disclosure generally relates to methods and systems of using water clusters and specifically to methods and systems of utilizing water clusters and their vibronic interactions in a plurality of applications.

BACKGROUND OF THE DISCLOSURE

[0003] Water covers two-thirds of the globe and constitutes seventy percent of our body weight.

Life on Earth would not exist without it. Water vapor in Earth's atmosphere may be one of the most significant greenhouse gases (see LM. Held and B.J. Soden, "Water vapor feedback and global warming", Annual Review of Energy and the Environment. 25, 441-475 2000). Small polyhedral clusters of water molecules, for example, as illustrated in FIGs. 1 and 2, have been experimentally identified as being potentially significant to the hydration and stabilization of bio-molecules (see M.M. Teeter, Proc. Natl. Acad. Sci. 81, 6014, 1984), proteins (see T. Baker et al., Crystallography in Molecular Biology, D. Moras et al., Eds., Plenum, New York), DNA (see L.A. Lipscomb et al., Biochemistry 33, 3649, 1994), and DNA-drug complexes (see S. Neidle, Nature 288, 129, 1980). Such examples indicate the tendency of water pentagons, illustrated in FIG. 1, to form closed geometrical structures like the pentagonal dodecahedron illustrated in FIG. 2. It has also been suggested that water clusters may play a fundamental role in determining biological cell architecture (see J.G. Watterson, Molec. And Cell. Biochem. 79, 101, 1988). While much of the human body is water by weight, much of that water may not be ordinary bulk liquid, but instead, nano-clustered or "restructured" water which affects bio-molecular processes ranging from protein stability to enzyme activity (see Finney et al., "The role of water perturbations in biological processes", Water and Aqueous Solutions, pp. 227-244, 1986). For example, nano-structured water in the form of water clusters has been found to congregate in the confined cavities of proteins and other bio-molecules, as illustrated in FIG. 3, where a cluster of water molecules interacts with a protein amino-acid group.

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[0004] An area of scientific interest in water clusters centers around their possible role in atmospheric and environmental phenomena, including global warming (see, for example, H. Carlon, J. Appl. Phys. 52, 3111, 1981), as well as by their relevance to the structure and properties of liquid water and ice (see F. N. Keutsch and R. J. Sakally, Proc. Natl. Acad. Sci. 98, 10533, 2001). Experiment and theory seem to indicate that not only can water clusters be produced, but they also exist optimally in certain "magic numbers" and configurations of water molecules (see, for example, Haberland et al., Electronic and Atomic Collisions, Elsevier, NY, 597, 1984). More prominent among the magic-number water clusters are those possessing an approximately pentagonal dodecahedral structure. Ideally, these water clusters have a closed, icosahedral symmetry formed by twenty hydrogen-bonded water molecules, for example, with their oxygen atoms at the vertices of 12 concatenated pentagons and with 10 free exterior hydrogen atoms. FIG. 2 depicts a protonated water cluster, (H ₂ O) ₂ iH ⁺ , which occurs as the dominant molecular species in a variety of experiments (see, for example, M. Miyazaki et al., Science 304, 1135, 2004). Its clathrate structure - a hydronium ion, H ₃ O ⁺ , or neutral water molecule plus proton H ⁺ trapped in the dodecahedral cage (see, for example, M. Miyazaki et al., Science 304, 1135, 2004) - is the typical protonated water cluster prototype.

[0005] Density-functional molecular-orbital calculations for the archetype (H ₂ O) _2I H ⁺ cluster of FIG.

2 yielded a set of molecular-orbital energies, shown in FIG. 4. In this embodiment, the lowest unoccupied molecular orbital (LUMO) energy levels correspond to the large, delocalized "S"-, "P"-, "Z ⁾ "- and "F'-like cluster wave-functions illustrated in FIG. 5. The iS-like LUMO level is separated from the highest occupied molecular orbital (HOMO) level by an energy gap of nearly 3 electron-volts (eV). The low-frequency vibrational modes of the (H ₂ O) ₂ iH ⁺ cluster have also been computed, producing, in one embodiment, the spectrum illustrated in FIG. 6 Of particular interest is the lowest frequency manifold of cluster modes between 1.5 and 6 terahertz (THz) (about 50 to 200 cm ^"1 ). The vectors in FIG. 7 illustrate the 1.56 THz "squashing" mode of the otherwise ideally symmetrical dodecahedral cluster (illustrated by FIG. 8), with a large-amplitude vibration of the clathrated hydronium oxygen atom coupled to breathing vibrations of the cluster "surface" oxygen atoms. O-H "stretching" and "bending" vibrational modes occur at much higher frequencies (not shown) spanning the broad infrared region of the spectrum. The 0.5-32 THz (about 50 to 1060 cm ^"1 ) manifold is thought to be due to water molecule clustering. Density-functional calculations for larger water clusters such as that illustrated in FIG. 9, and even for the simple pentamer in FIG. 1 , indicate similar manifolds of cluster terahertz vibrational modes, except that they extend to as low as 0.5 THz for the largest clusters.

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[0006] Anomalous emission and absorption of far-infrared and sub-millimeter (THz) radiation from the atmosphere were first identified by Gebbie (see H. A. Gebbie, Nature 296, 422, 1982), as possibly associated with aerosols of water clusters undergoing solar optical pumping. It is thought that at sea-level densities, such aerosols are separated by 10 ⁴ times their cluster radii and, under this condition of isolation, can be pumped by photons into vibrational modes of lowest frequency analogous to a Bose-Einstein condensation, thus acquiring giant electric dipoles. Their interaction with radiation is thereby greatly enhanced. For example, atmospheric aerosol absorption at 50 cm ^"1 is comparable with that of a water molecule rotation line at 47 cm ^"1 , which has a dipole moment of 1.85 Debyes in an air sample containing 10 ¹⁷ cm ^"3 water molecules. Even if the aerosol density of water clusters is only approximately 10 ⁴ cm ^"3 (see H. Pruppacher and J. D. Klett, Microphysics of Clouds and Precipitation, Reidel, Dordrecht, 1978), then an effective aerosol transition moment of 10 ⁶ Debyes can be inferred. In other words, this greatly enhanced submillimeter (THz) absorption and emission from comparatively low-density aerosols can be attributed to solar optical pumping, cooperative stimulated emission, and maser action of the constituent water clusters.

[0007] The electronic structure (as illustrated in FIGs. 4 and 5) and vibrational spectrum (as illustrated in FIG. 6) of the (H ₂ O) _2I H ⁺ and other similar clusters can satisfy the conditions for intense optical absorption and Terahertz emission. First, the near-ultraviolet optical pumping of an electron from the HOMO to LUMO can put the electron into the bound S-like cluster molecular orbital mapped in FIG. 5. This is a stable excited state of the cluster. Near-infrared absorption can then excite the LUMO S-like electron to the nearby unoccupied /Mike orbital (as illustrated in FIGs. 4 and 5). There are three nearly degenerate P-like cluster molecular orbitals, analogous to the degenerate p _τ , p _y , and p _z orbitals of an atom. Unlike an atom, however, the P _x , P _y , P ₂ near-degeneracy in the water cluster subjects it to the dynamic Jahn- Teller (DJT) effect (see I. Bersuker et al, "Vibronic Interactions in Molecules and Crystals", Springer- Verlag, 1989), where the cluster attempts to remove the degeneracy and lower its energy through vibronic coupling and symmetry breaking. Near-infrared promotion of the optically pumped electron between the closely spaced P-like and D-like cluster energy levels (illustrated in FIG. 4) may also be likely.

[0008] Even in the absence of DJT coupling, excitations within the LUMO manifold can decay vibronically due to the mixing of electronic states. The vibrations here are the Terahertz modes that are the lowest-frequency (H ₂ O) _2I H ⁺ cluster modes, like the 1.56 THz "squashing mode" illustrated in FIGs. 7 and 8. The predicted electric dipole moment of the (H ₂ O) ₂ iH ⁺ cluster in its optically pumped state is nearly 10 Debyes, as compared with the 1.85 Debye moment for a single water molecule. As shown by the vectors in FIG. 7, the large-amplitude Terahertz vibration of the clathrated hydronium oxygen atom, coupled to

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breathing modes of the cluster "surface" oxygen atoms, produces an oscillating large electric dipole moment that constitutes the transition moment for Terahertz emission when the cluster is optically pumped. The excited electron in the LUMO manifold may be weakly bound compared to the cluster hydrogen-bonded "valence" electrons below the LUMO level. In fact, the occupied cluster molecular orbital levels below the HOMO (as illustrated in FIG. 4) are, in some embodiments, analogous to the 'Valence band" of a semiconductor, whereas the LUMO manifold is, in some embodiments, analogous to a semiconductor "conduction band". Thus in (or similar) clusters, the ensemble of optically pumped electrons in the LUMO manifolds, loosely bound to the vibrationally activated, positively charged (H ₂ O) _2I H ⁺ molecular ion "cores", can effectively constitutes a "plasma". An alternative scenario is to view an electron in the LUMO manifold "conduction band", responsible for the large dipole moment of the clusters, as oscillating in the reference frame of the (H ₂ O) _2I H ⁺ ion core. Since the positive charge of the (H ₂ O) _2I H ⁺ cluster is due to the "extra" proton, an even simpler picture is a "hydrogenic plasma" model, in which the aerosol is modeled as electrons loosely bound to protons in large-radius "Rydberg-like" S-, P-, D- or F-like orbits.

SUMMARY OF THE DISCLOSURE

[0009] The present disclosure describes certain preferred embodiments of water clusters and their applications. These water clusters can have good symmetry (illustrated in FIGs. 1 and 2) and may be present in natural systems or produced in engineered systems. In some embodiments, the water clusters' molecular vibrations are coupled to the water clusters' electronic states (hereafter referred to as "vibronic interactions"). Embodiments of these water clusters may be promoted for applications in the areas of environmental remediation, clean energy production, terahertz radiation technologies, chemical synthesis and reactivity and pharmaceutical and biomedical technologies. Water clusters include protonated water clusters, negatively charged water clusters, and neutral water clusters. These three species of water clusters are hereinafter generally referred to as "water clusters". Protonated or positively charged water clusters, and negatively charge water clusters, are hereinafter generally referred to as "charged water clusters".

[0010] In one aspect, a method for removing at least one water cluster from the atmosphere includes injecting at least one electron into the atmosphere, the atmosphere including a plurality of water clusters, wherein the at least one injected electron interacts with the plurality of water clusters causing at least one water cluster to break down. In one embodiment, the method includes injecting at least one electron into the troposphere, the troposphere including the plurality of water clusters. In another embodiment, the method

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includes injecting at least one electron from a photoelectron-emitting material on an aircraft, the photoelectron-emitting material releasing at least one electron under radiation.

[0011] In another aspect, a method for removing heat stored in carbon dioxide in the atmosphere includes injecting at least one electron into the atmosphere, the atmosphere including a plurality of water clusters, wherein the at least one injected electron attaches onto at least one of the plurality of water clusters to form at least one charged water cluster; the at least one charged water cluster attracting and absorbing carbon dioxide from the atmosphere and converting heat stored in the carbon dioxide into radiation. In one embodiment, the method includes applying radiation to the plurality of water clusters, the radiation at a frequency in the range of 0.5 terahertz to 32 terahertz. In another embodiment, the method includes injecting at least one electron into the troposphere, the troposphere including a plurality of water clusters, wherein the at least one injected electron attaches onto at least one of the plurality of water clusters to form at least one charged water cluster; the at least one charged water cluster attracting and absorbing carbon dioxide from the troposphere and converting heat stored in the carbon dioxide into radiation.

[0012] In yet another aspect, a method for clean energy production includes applying laser stimulation to water vapor to generate terahertz radiation energy from at least one water cluster included in the water vapor, and extracting the terahertz radiation energy from the at least one water cluster. In one embodiment, the method includes extracting the terahertz radiation energy from at least one water cluster via frequency conversion.

[0013] In still even another aspect, a method for clean energy production includes applying stimulation to at least one water cluster to induce vibration of the at least one water cluster at a frequency in the range of 0.5 terahertz and 32 terahertz; and impacting the at least one water cluster on a hydride surface to induce nuclear fusion, the nuclear fusion releasing energy. In one embodiment, each of the at least one water cluster is a heavy water cluster comprising Deuterium. In another embodiment, the nuclear fusion is selected from the group consisting of Deuterium-Deuterium fusion and Hydrogen-Hydrogen fusion.

[0014] In still yet another aspect, a method for releasing trapped gas from clathrate hydrate includes applying, to clathrate hydrate, radiation at a frequency in the range of 0.5 terahertz to 32 terahertz, the clathrate hydrate including trapped gas, and releasing, via energy gap reduction associated with the clathrate hydrate and induced by the radiation, at least a portion of the trapped gas. In one embodiment, the trapped gas is methane.

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[0015] In another aspect, a method for producing hydrogen gas from water vapor, comprising impacting at least one water cluster onto an electrically-charged palladium surface, the surface catalyzing the dissociation of the at least one water cluster to produce hydrogen gas.

[0016] In another aspect, a method for generating terahertz radiation, comprising applying a laser pulse to water clusters in water vapor. In one embodiment, the method includes applying a laser pulse to water clusters in water vapor injected from a gas jet nozzle.

[0017] In still another aspect, a method for using terahertz radiation from water clusters for communications includes generating radiation from water clusters in water vapor, tuning the radiation to a frequency in the range of 1.3 terahertz to 1.5 terahertz; and applying the tuned radiation as a carrier wave for a communications signal. In one embodiment, the method includes generating radiation from water clusters in water vapor in the atmosphere.

[0018] In another aspect, a method for causing malfunction in an electronic system includes generating a laser pulse from a plurality of water clusters at a frequency in the range of 0.5 terahertz to 32 terahertz, and applying the laser pulse at an electronic system to cause malfunction in the electronic system. In one embodiment, the method includes applying the laser pulse at an electronic system, the application being substantially silent, odorless, visually undetectable and harmless to a human body. In another embodiment, the method includes deactivating the electronic system. In still another embodiment, the method includes creating distortion in an electronic system, the electronic system being a radar detection system.

[0019] In yet another aspect, a method of increasing reactive behavior in chemical reactions associated with water, comprising applying radiation, at a frequency in the range of 0.5 terahertz to 32 terahertz, to a plurality of water clusters in the chemical reaction. In one embodiment, the chemical reaction represents the breakdown of biological material, via interaction with the water clusters, to produce a bio-fuel.

[0020] In still another aspect, a method for imparting a biocidal property against at least one pathogenic agent includes applying at least one negatively-charged water cluster to at least one pathogenic agent. In one embodiment, the method includes adding at least one water cluster to the at least one pathogenic agent, the water cluster including a bicatalytic element clathrated by the water cluster. In another embodiment, the method includes adding at least one water cluster to the at least one pathogenic agent, the water cluster including silver clathrated by the water cluster. In still another embodiment, the method

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delivering the at least one water cluster via a delivery medium, the delivery medium is selected from the group consisting of a spray, an emulsion, a nano-spray and a nano-emulsion.

[0021] In still another aspect, a method for delivering a chemical to a region of biological tissue, comprising combining a chemical with at least one water cluster to form at least one water cluster micelle, and delivering the at least one water cluster micelle to a region of biological tissue. In one embodiment, the chemical is a pharmaceutical agent. In another embodiment, the region of biological tissue is a region of a brain. In another embodiment, the method includes delivering the at least one water cluster micelle across a blood-brain barrier to the region of the brain.

[0022] In yet another aspect, a method for transdermal delivery of a chemical includes applying at least one water cluster to clathrate a chemical, and delivering the clathrated chemical through cellular skin. In one embodiment, the method includes activating the chemical, via the at least one water cluster, for interaction with receptor sites upon delivery. In another embodiment, the method includes activating the chemical, via application of radiation at a frequency in the range of 0.5 terahertz to 32 terahertz on the at least one water cluster, for interaction with receptor sites upon delivery. In still another embodiment, the method includes removing free radicals encountered in the skin. In still even another embodiment, the method includes reducing water evaporation through the skin. In one embodiment, the method includes comprises deactivating, via additional water clusters, lipid hydrophobes in the skin, the lipid hydrophobes hindering transdermal delivery of the chemical. In still yet another embodiment, the chemical is a pharmaceutical compound.

[0023] In one aspect, a method for promoting proper protein folding in a biomedical treatment includes applying at least one water cluster to clathrate a pharmaceutical compound, delivering the clathrated pharmaceutical compound to a protein, and providing, via the clathrated pharmaceutical compound, a water cluster interface with the protein, and restoring a proper protein folding to the protein. In one embodiment, the method includes applying a radiation at a frequency in the range of 0.5 terahertz to 32 terahertz. In another embodiment, the protein is part of a cancer cell.

[0024] In still another aspect, a method for spacecraft propulsion, includes extracting a plurality of water clusters, the plurality of water clusters including charged water clusters. The method includes accelerating the charged water clusters. The method includes emitting the charged water clusters to generate thrust for a spacecraft. In one embodiment, the method includes extracting the plurality of water clusters

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from interstellar space. In another embodiment, the method includes passing water vapor through a plurality of multi-aperture grids. In still another embodiment, the method includes applying a potential difference between a first grid of the plurality of multi-aperture grids and a second grid of the plurality of multi-aperture grids. In yet another embodiment, the method includes accelerating each of the charged water clusters to an energy level of at least 1 kilo-electron-volt.

BRIEF DESCRIPTION OF THE FIGURES

[0025] The foregoing and other objects, aspects, features, and advantages of the disclosure will become more apparent and better understood by referring to the following description taken in conjunction with the accompanying drawings, in which:

[0026] FIG. 1 depicts an embodiment of a pentagonal cluster of water molecules.

[0027] FIG. 2 depicts an embodiment of a pentagonal dodecahedral (H ₂ θ) ₂ iH ⁺ cluster.

[0028] FIG. 3 depicts an embodiment of a water cluster interacting with a protein amino-acid group.

[0029] FIG. 4 depicts an embodiment of a density-functional molecular-orbital energies of the

(H ₂ O) _2I H ⁺ cluster.

[0030] FIG. 5 depicts an embodiments of S- like, P- like, D- like, and F-like LUMO wavefunctions of the (H ₂ O) ₂ iH ⁺ cluster.

[0031] FIG. 6 depicts an embodiment of a computed vibrational spectrum of the (H ₂ O) ₂ iH ⁺ cluster.

[0032] FIG. 7 depicts an embodiment of a Terahertz vibrational mode of a (H ₂ O) ₂ iH ⁺ cluster.

[0033] FIG. 8 depicts embodiments of vibrational modes of a pentagonal dodecahedron.

[0034] FIG. 9 depicts an embodiment of a large water cluster;

[0035] FIG. 10 is a graph depicting an embodiment of a lowering of the energy barrier of a chemical reaction by a water cluster;

[0036] FIG. 11 depicts an embodiment of a water-cluster micelle;

[0037] FIG. 12 is a flow diagram depicting an embodiment of steps of a method for using terahertz radiation from water clusters for communications;

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[0038] FIG. 13 is a flow diagram depicting an embodiment of steps of a method for promoting proper protein folding in a biomedical treatment; and

[0039] FIG. 14 is a flow diagram depicting an embodiment of steps of a method for spacecraft propulsion.

[0040] The features and advantages of the present disclosure will become more apparent from the detailed description set forth below when taken in conjunction with the drawings, in which like reference characters identify corresponding elements throughout. In the drawings, like reference numbers generally indicate identical, functionally similar, and/or structurally similar elements.

DETAILED DESCRIPTION

[0041] The present disclosure discusses certain preferred embodiments of water clusters wherein their molecular vibrations are coupled to the water clusters' electronic states (hereafter referred to as "vibronic interactions"). In some embodiments, the molecular vibrations are in the 0.5 - 32 terahertz (THz) frequency range. Water clusters characterized by such interactions may be leveraged as active agents in various applications. They can be found in solid, liquid and gaseous states of water, both on earth and in space, and can be distinguished from typical masses or molecules of water by having properties, such as those characterized by vibronic interactions. Due to these properties, the water clusters of this disclosure may also be considered as representing a fourth state or phase of water, and is distinguished from a simple collection of water molecules such as a droplet. Water clusters may be found in natural systems, which includes the earth's atmosphere, in biological systems and reservoirs of water. Water clusters may also be produced in engineered systems, including, but not limited to, pressurized water vapor cells, nano- electrospray apparatus, jet nozzle systems, ion mobility drift tube apparatus, water-in-oil nano-emulsion formulations (see, for example, US Patents 5,800,576 and 5,997,590), molecular beam apparatus and supercritical water cells.

[0042] In some embodiments, the water clusters may have high symmetry and possess pentagonal or pentagonal dodecahedral structures, as illustrated in FIGs. 1 and 2 respectively. In some of these embodiments, water clusters are globular clusters containing up to 100 water molecules (as illustrated in FIG. 9). Preferred embodiments of a water cluster may include twenty or twenty-one water molecules. In one embodiment, a pentagonal dodecahedral cluster can have a closed, icosahedral symmetry formed by twenty hydrogen-bonded water molecules. The associated oxygen atoms are at the vertices of twelve concatenated pentagons and there are ten free exterior hydrogen atoms. FIG. 2 shows an embodiment of a protonated

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water cluster, (H ₂ O^oH ₃ O ⁺ or (H ₂ O) _2I H ⁺ . This has been identified as a dominant molecular species in a variety of experiments (see, for example, Hermann et al., Chem. Phys. 76, 2031, 1982).

[0043] Calculated density-functional molecular-orbital levels for the (H ₂ θ) ₂ iH ⁺ cluster are shown in

FIG. 4. The lowest unoccupied molecular orbital (LUMO) energy levels correspond to the large, delocalized "S"-, "F'-, "D"- and "F'-like cluster wave-functions depicted in FIG. 5. The "5"-like LUMO level is separated from the highest occupied molecular orbital (HOMO) level by an energy gap of nearly 3 eV. The vibrational modes of this cluster have also been computed, an embodiment of the spectrum shown in FIG. 6. Of particular relevance to certain applications of this disclosure is the lowest frequency manifold of cluster modes between 1.5 and 6 THz (about 50 to 200 cm ^"1 ). The vectors in FIG. 7 show a typical "squashing" mode of the dodecahedral cluster, with a large-amplitude vibration of the clathrated hydronium oxygen atom coupled to breathing vibrations of the cluster "surface" oxygen atoms. Water-cluster "librational modes" are shown in FIG. 6 to occur at higher frequencies up to 32 THz. The 1.5-32 THz (about 50 to 1060 cm ^"1 ) manifolds may be characteristic of water molecule clustering. Density-functional molecular-orbital calculations for larger water clusters, for example, the embodiment shown in Fig 9, result in similar manifolds of terahertz modes extending to 0.5 THz for the larger clusters.

[0044] Water clusters containing stable pentagonal dodecahedral water structures may be produced by a variety of methods. In liquid water, pentagonal dodecahedral structures may form transiently, but can be unstable. Liquid water can, in one embodiment, be modeled as a collection of pentagonal dodecahedra in which inter-structure interactions are approximately as strong as, or stronger than, intra-structure interactions. To produce stable pentagonal dodecahedral water structures from liquid water, the long-range inter-structure interactions present in liquid water may be disrupted in favor of the intra-structure association. Any of a variety of methods, including physical, chemical, electrical, and electromagnetic methods, can be used to accomplish this. For example, a method of isolating a pentagonal dodecahedral water structure is simply to extract twenty or twenty-one water molecules into a single nano-droplet. Water clusters of twenty or twenty- one water molecules are two preferred embodiments.

[0045] Other methods of producing pentagonal dodecahedral water structures include passing water vapor through a hypersonic nozzle (see, for example, Lin, Rev. Sci. Instrum. 44:516, 1973). Other methods of hypersonic nozzling may also apply. For example, an improved hypersonic nozzling method for preparing pentagonal dodecahedral water structures may include a hypersonic nozzle with a catalytic material such as nickel or a nickel alloy positioned and arranged so that, as water passes through the nozzle, the water comes into contact with reacting orbitals on the catalytic material. The catalytic material may

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disrupt inter-cluster bonding by sending electrons into anti-bonding orbitals without interfering with intra- cluster bonding interactions.

[0046] Chemical methods for producing water clusters comprising pentagonal dodecahedral structures can include the use of surfactants and/or clathrating agents. Electrical methods may involve inducing electrical breakdown of inter-cluster interactions by providing an electrical spark of sufficient voltage and appropriate frequency. Electromagnetic methods can include application of microwaves of appropriate frequency to interact with the "squashing" vibrational modes of inter-cluster oxygen-oxygen interactions. Also, since it is known that ultrasound waves can cavitate (produce bubbles in) water, it is predicted that inter-cluster associations can be disrupted ultrasonically without interfering with intra-cluster interactions. Finally, various other methods have been reported for the production of pentagonal dodecahedral water structures. Such methods include ion bombardment of ice surfaces (see Haberland, Electronic and Atomic Collisions, ed. by Eichler et al, Elsevier, Ansterdam, pp. 597-604, 1984), electron impact ionization (see, for example, Lin, Rev. Sci. Instrum. 44:516, 1973), and near-threshold vacuum-UV photoionization of neutral clusters (see, for example, Shinohara et al. Chem. Phys. 83:4183, 1985).

[0047] In some embodiments, it may be desirable to ionize the pentagonal dodecahedral water structures (e.g., by passing them through an electrical potential after they are formed) to increase their kinetic energy and reactivity through coulombic repulsion.

[0048] Water cluster vibrational modes such as that illustrated in FIG. 6 may be induced or promoted through application of an external electromagnetic field and/or through the intrinsic action of the dynamical Jahn-Teller (DJT) effect using methods including photoelectric stimulation, addition of electronic charge, exposure to terahertz radiation, design of specific water-in-oil nano-emulsion formulations, design of certain clathrates in water cluster cages (i.e. silver) and contact with certain electron donning materials (i.e. nickel). The Jahn-Teller (JT) effect is known to cause symmetrical structures to distort or deform along symmetry-determined vibrational coordinates (Q _s ) as illustrated in FIG. 10. Potential energy minima corresponding to the broken-symmetry forms can arise, and the structure may either settle into one of these minima (static Jahn-Teller effect), or oscillate between or among such minima, such as vibrating along the relevant vibrational coordinates (DJT effect).

[0049] DJT-induced vibrational oscillations in certain water clusters can significantly lower the energy barrier for chemical reactions involving such clusters (illustrated in FIG. 10). Specifically, the present disclosure teaches that water clusters (or aggregates thereof) having a ground-state electronic structure characterized by a manifold of fully occupied molecular orbitals (HOMO) separated from a manifold of

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unoccupied molecular orbitals (LUMO) by an energy gap (as illustrated in FIG. 4) can be made to have enhanced reactivity characteristics if the degenerate LUMO states (as illustrated in FIG. 5) are occupied via HOMO-to-LUMO electromagnetic (optical) excitation or through the external addition of electronic charge. This can lead to distortive symmetry breaking and DJT-induced vibronic oscillations.

[0050] A large-amplitude Terahertz vibration of the clathrated hydronium oxygen atom, coupled to breathing modes of the cluster "surface" oxygen atoms (as illustrated in FIG. 6), can produce an oscillating large electric dipole moment that constitutes the transition moment for Terahertz emission when the cluster is optically pumped. Thus water vapor populated by such water clusters may be strong sources of terahertz radiation between approximately 1.5 and 32 TFIz (as illustrated in FIG. 7).

[0051] To estimate the Terahertz emission power of a water cluster at 1.5 THz, we begin with the standard formula for electromagnetic radiation power emission from an oscillating electric dipole (in cgs units), P = p ² ω ⁴ /3c ³ , where p is the dipole moment, ω is the (angular) frequency of the dipole vibration - in a protonated water cluster (as illustrated in FIG. 2)and the "squashing vibration shown in FIG. 7 - and c is the velocity of light. The dipole moment of a protonated water cluster (H2O) ₂ iH ⁺ in its ground state is approximately 10 Debyes (IDebye = 10 ^~18 esu-cm). Under electromagnetic (optical) excitation across the HOMO-LUMO energy gap of such a cluster or by external addition of electrons to the LUMOs (as illustrated in FIG. 3), p can approach 50 Debyes, i.e. the effective dipole moment of an optically pumped or negatively-charged water cluster is much larger than that of the ground state. Therefore at Terahertz frequencies, e.g. 1.5 THz, the emission power output of a single water cluster is typically of the order of (converting cgs to MKS units) 10 ^"21 watt/cluster. For a room-temperature, 40 torr pressure density of 10 ¹² water clusters/cm ³ , this yields a potential Terahertz emission power of approximately 10 ^"9 watt or one nanowatt/cm ³ . Therefore a one cubic meter water- vapor chamber containing such a density of water clusters could potentially produce a milliwatt of Terahertz radiation, i.e. comparable to that produced by a commercially available semiconductor Terahertz source. Raising the pressure of the chamber should significantly increase the water cluster population, approaching 10 ¹⁵ /cm ³ at 100 torr. This would imply 10 ^"6 watt/cm ³ or one watt/m ³ , which may exceed the power output of most commercially available Terahertz sources.

[0052] In this disclosure, embodiments of methods and systems of utilizing water clusters and their vibronic interactions are disclosed in connection with a number of applications. Areas of interest

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include environmental remediation, clean energy production, terahertz radiation technologies, chemical synthesis and reactivity, and pharmaceutical and biomedical technologies.

ENVIRONMENTAL REMEDIATION

[0053] Atmospheric water can be a significant contributor to global warming, compared with carbon dioxide and methane. In one report, water vapor causes 36-70% of the greenhouse effect on Earth, excluding clouds, while carbon dioxide (CO ₂ ) causes only 9-26%, and Methane (CH ₄ ), only 4-9%. Although increases of CO ₂ are known to elevate the greenhouse effect and thus global warming, the contribution of atmospheric water is not as commonly discussed partly because unlike most other gases, the distribution of atmospheric water can vary greatly with altitude, terrestrial location, and across time, and water vapor can change between the liquid and solid phases at terrestrial temperatures. For example, slight increases of ocean temperature may produce significant increases in the evaporation of water molecules into the atmosphere. This is in addition to growing man-made combustion sources of water vapor, such as from industry, terrestrial vehicles, ships and aircraft. Even fuel cells, such as used in "clean energy" vehicles, produces water vapor.

[0054] Water vapor is typically viewed as a gas comprising distinct H ₂ O molecules. However, from experimental research at the UK Rutherford Appleton Laboratories and theoretical models developed at MIT and HydroElectron Ventures, Inc. (HEV), atmospheric water vapor can be a natural source of clusters of water molecules, especially protonated water clusters such as (H ₂ θ) ₂ iH ⁺ . A water cluster, such as that illustrated in FIG. 7, may store more heat than the sum total from separate water molecules because of the water cluster's vibrational degrees of freedom, which may be shown by unique cluster "surface" vibration vectors. The heat storage capacities of such clusters can approach that of bulk water. Thus, even a modest collection of water clusters in the troposphere can contribute significantly to the greenhouse effect and may explain why water vapor can be a significant greenhouse gas.

[0055] While increases of atmospheric CO2 can contribute to warming of the oceans and therefore increases in atmospheric water clusters, CO ₂ can directly interact with and be captured by water clusters, forming clusters such as (H ₂ O) _n C(V, the analogue of solvated CO ₂ . The capture of CO ₂ by water clusters increases the cluster heat storage capacities because of the additional vibrational modes OfCO ₂ . Water clusters, including clusters such as (H ₂ θ) _n Cθ ₂ ^~ , have the unique property that their vibrational frequencies can extend into the terahertz (THz) region of the electromagnetic spectrum. Thus, atmospheric water vapor including such clusters can be a strong absorber of Terahertz radiation. Water clusters in general are

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relatively strong absorbers and emitters in the terahertz region and relatively strong absorbers of infrared (heat) radiation. However, water clusters in general do not radiate heat as efficiently. We leverage these properties of water clusters in applications that may help reduce global warming.

[0056] A method for reducing the greenhouse effect and global warming may involve removing water clusters from the atmosphere. In some embodiments, the addition of electrons to water clusters can break the water clusters down into separate water molecules. This can reduce the contribution of water molecule clustering to atmospheric heat storage. In one embodiment, a method for removing at least one water cluster from the atmosphere includes injecting one or more electrons into the atmosphere, the atmosphere including a plurality of water clusters. The one or more injected electrons interacts with the plurality of water clusters causing one or more water clusters to break down. Each of these water clusters can be a protonated water cluster or any other embodiment of a water cluster.

[0057] In another embodiment, the method may target the troposphere component of the Earth's atmosphere, the troposphere including the plurality of water clusters. In still another embodiment, one or more atmospheric layers in the Earth's atmosphere may be targeted for electron injection. In some embodiments, the method includes injecting at least one electron from a photoelectron-emitting material. The photoelectron-emitting material may be mounted on an aircraft, balloon, or any high-altitude structures or media. Any type or form of aircraft, balloon and structures may be located in the appropriate atmospheric layer or layers. The photoelecfron-emitting material releases one or more electrons when subject to radiation. The photoelectron-emitting material may be fabricated as a panel or any form or type of structure or coating. In one embodiment, the radiation is solar radiation. This method could be accomplished, for example, safely from the many commercial aircraft flying daily through the troposphere by exposing photoelectron-emitting panels that would release electrons under solar radiation once the aircraft reaches a specific altitude. Ozone may be a byproduct of this process but tropospheric ozone is known to be beneficial. In addition, deployment of Terahertz radiation sources in certain embodiments may also assist in breaking down the atmospheric, heat-storing water clusters.

[0058] Through research collaboration between the Center for Terahertz Research at Rensselaer

Polytechnic Institute (RPI) and HEV, it is shown that terrestrial ambient water vapor can also be a strong emitter of harmless (non-ionizing) Terahertz radiation which may be associated with water cluster Terahertz vibrational modes like that shown in FIG. 7. Therefore, a method of converting heart to terahertz radiation may be beneficial to mitigating atmospheric warming.

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[0059] As described above, CO2 molecules can directly interact with and be captured by water clusters. A method of reducing heat stored in CO ₂ may help reduce the greenhouse effect. In one embodiment, the method includes injecting one or more electrons into the atmosphere, the atmosphere including a number of water clusters. In another embodiment, the method may specifically focus on the troposphere of the Earth's atmosphere, the troposphere including the plurality of water clusters. In still another embodiment, one or more atmospheric layers in the Earth's atmosphere may be targeted for electron injection. The one or more injected electrons may attach onto at least one water cluster to form at least one charged water cluster. A charged water cluster, as formed, can attract and absorb carbon dioxide from the atmosphere. The heat stored in the carbon dioxide can then be converted into Terahertz radiation. Here, heat can be converted vibronically to Terahertz radiation and harmlessly removed from the atmosphere.

[0060] In some embodiments, Terahertz radiation is applied to the plurality of water clusters, the applied radiation at a frequency in the range of 0.5 terahertz to 32 terahertz. The applied radiation can help CO ₂ interact with the water clusters, for example, forming water clusters such as (H ₂ O) _n CO ₂ ^" . Moreover, the applied radiation may help activate the removal of heat through Terahertz radiation. In one of these embodiments, after the removal of an amount of heat through radiation, the water clusters may be removed. One method of removing such clusters is the method of injecting electrons into water clusters to break up the clusters, as discussed above. Some of these water clusters may absorb and retain heat in the atmosphere if they remain in sufficient concentration in the atmosphere.

CLEAN ENERGY PRODUCTION

[0061] A water cluster can store more energy than do the separate water vapor molecules because of the many vibrational degrees of freedom. The water cluster may be in a 1.5 THz mode, as shown in FIG. 7, with large-amplitude excursions of the "surface oxygen" atoms. It is possible to identify the significant vibrational energy exchange between such clusters and their ambient surroundings, as well as the catalytic vibronic energy exchanges that occur when such clusters chemically interact with other molecules and at material interfaces.

Biofuel Production

[0062] In the oxidation/combustion of carbon compounds such as hydrocarbon fuels, water-cluster orbitals on the cluster surface oxygen atoms can overlap with the reactive fuel carbon (e.g. pπ) orbitals, promoting oxidation. Because of the potentially significant displacements (large Q _s ) of water-cluster surface

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oxygen atoms in the Terahertz vibrational modes, the energy barrier for an expulsion of water oxygen or OH radicals and their oxidative and reactive carbon atoms may be lowered from Eba _m e _r to E'ba _m e _r , as illustrated in FIG. 10. The use of water clusters in nano-emulsions along with their direct injection to increase efficiency of diesel combustion while reducing pollutants are described in U.S. Patents 5,800,576 and 5,997,590. Biological enzymes may not be able to function without at least a monolayer (clusters) of water molecules at the interface, which is key to the hydrolysis of cellulose to glucose. Water clusters may also be used to catalyze the breakdown of biological material, such as switchgrass cellulose. In one embodiment, the water clusters' vibronic interactions may be activated to allow for the efficient breakdown of bio-fuel stocks, or more generally, biological material. This method can be a more efficient process for producing bio-fuels.

Hydrogen Production

[0063] In some embodiments, a system and method for producing hydrogen fuel from water involves nano-electrolysis. In this clean energy production application, experiments performed at McGiIl University indicates that mass-spectrometrically selected protonated water clusters impacting thin, negatively charged metallic membranes can strip hydrogen from the clusters. The water-cluster and membrane interface represents part of a nano-electrolytic system for the nano-electrolysis.

[0064] In one embodiment, a method for producing hydrogen gas from water vapor includes impacting at least one water cluster onto an electrically-charged palladium surface, the surface catalyzing the dissociation of the at least one water cluster to produce hydrogen gas. In another embodiment, the water cluster may be a protonated water cluster or any other type of water cluster. The hydrogen gas may pass through the membrane and be collected. The collected hydrogen gas can then be used as fuel.

Terahertz Radiation Energy

[0065] Water clusters have the unusual property that their vibrational frequencies extend into the

Terahertz region of the electromagnetic spectrum. Through research collaboration between the Center for Terahertz Research at RPI and HEV, it is shown that laser-stimulated water vapor is a strong emitter of Terahertz radiation, and believed to be associated with water cluster Terahertz vibrational modes like the 1.5 THz mode shown in FIG. 7.

[0066] In one embodiment, a method for clean energy production includes applying laser stimulation to water vapor to generate Terahertz radiation energy from at least one water cluster included in the water

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vapor, and extracting the Terahertz radiation energy from the at least one water cluster. The Terahertz radiation energy from the water clusters may be extracted either directly or through frequency conversion, and utilized. Any form or type of frequency conversion process may be used, for example, four wave mixing. In particular, non-degenerate four-wave mixing (ND-FWM) may be used.

Nuclear Fusion

[0067] In some embodiments, a method for clean energy production includes applying stimulation to at least one water cluster to induce vibration of the at least one water cluster at a frequency in the range of 0.5 terahertz and 32 terahertz. . In one embodiment, each of the water clusters is a heavy water cluster with Deuterium instead of Hydrogen. For example, ordinary hydrogen water clusters may be replaced with their heavy-water counterparts such as (D ₂ O) ₂ iD ⁺ . In another embodiment, the water clusters do not include Deuterium. Conditions for the water clusters may be induced, for example, to undergo significant low energy nuclear reactions. The conditions may include, for example, temperature, radiation and use of a catalyst. The nuclear water cluster Terahertz vibrations may be internally or externally stimulated.

[0068] In one embodiment, water clusters can be impacted onto a hydride surface to induce nuclear fusion. The impacted water clusters may be protonated water clusters. Energy released from the nuclear fusion may then be collected and utilized as a clean energy. The fusion may be either Deuterium-Deuterium fusion or Hydrogen-Hydrogen fusion. Such a use of water clusters may be a practical method of inducing nuclear fusion.

Gas Hydrate Liberation

[0069] One aspect of water cluster vibronic interaction relates to methods and systems for extracting gases, including methods and systems for extracting methane and other trapped gas from their hydrate cages. Gas hydrates, also referred to as clathrate hydrates, are crystalline combinations of one or more gases such as methane, natural gas and other hydrocarbon gas molecules of small linear dimension (i.e., C i -C ₄ or larger carbon containing molecules which have a maximum linear dimension of about 10 nanometers (100 Angstroms) such as neopentane) and water formed into a substance that may look like ice but can be unstable at standard temperature and pressure. The gas hydrate also may contain other light gases (CO ₂ , H ₂ S ₅ N ₂ , etc.). The gas molecules may be physically entrapped or engaged in the expanded lattice of the water network comprising hydrogen bonded molecules. The structure may be stable due to weak Van der Waals bonding between the gas and the water molecules and hydrogen-bonding between water molecules within the cage structure.

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[0070] Gas hydrates may be found under the ocean floor and in permafrost. Gas hydrate is increasingly being considered as a source of fuel to be tapped. Gas hydrates may occur abundantly in nature, both in Arctic regions and in marine sediments. Methane hydrate can be stable in ocean floor sediments at water depths greater than 300 meters and, where it occurs, it is known to cement loose sediments in a surface layer several hundred meters thick.

[0071] Natural gas may be produced economically from the methane and other gas hydrates on a large scale. The U.S. Geological Survey (USGS) estimates that the methane hydrates beneath U.S. waters can hold some 200 trillion cubic feet of natural gas, and may be enough to supply all the nation's energy needs for more than 2,000 years at current rates of use. These immense amounts of natural gas can have significant implications for energy resources and climate, but the nature of hydrates and their impacts on the environment are generally not well understood.

[0072] The presence of gas hydrates has several hazardous implications and environmental concerns. In the Gulf of Mexico, oil companies are drilling into water more than 1,000 meters deep and are starting to drill through layers of methane hydrate. This can cause the hydrate to dissociate. If the focus is limited to extracting the oil beneath the gas hydrate layers and/or appropriate precautions are not taken, gas may be released which can explode and cause drilling crews to lose control of their wells. Engineers are worried that unstable hydrate layers could give way beneath oil platforms or even play a role in triggering tsunamis. There is also concern that global warming could melt some shallow methane deposits, releasing millions of tons of this potent greenhouse gas into the air.

[0073] Gas hydrates have not been typically economical to harvest using other existing methods.

Supplying heat as steam at the bottom of a drill hole can be inefficient because of heat loss to the wall of the hole. Supplying electrical heat can also be inefficient because transmission of that heat to the water-hydrate interface would require a higher temperatures in the area of the heater. Physically mining the deposits and releasing/capturing the gas at the surface may be technically possible but can be economically prohibitive. Since the days of plentiful oil and gas may be numbered, and countries will require new energy sources to keep their economies moving, gas hydrates could be an answer. The worldwide amounts of carbon-based fuel bound in gas hydrates is estimated to total twice the amount of carbon-based fuel found in other known fossil fuels on Earth. This estimate was made with available information from U.S. Geological Survey (USGS) and other studies. Extraction of methane from hydrates could provide a useful energy resource. Additionally, other conventional gas resources currently trapped beneath methane hydrate layers in ocean sediments may yet be released.

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[0074] Research efforts have been directed to reducing the problems of gas hydrates in petroleum product lines, by either inhibiting the formation thereof or dissociating gas hydrates which are present and/or recovering the gases from the hydrates for beneficial use. For example, PCT application number PCT/US97/24202 reviews a variety of prior art research focused upon these. This reference discloses the use of electromagnetic radiation over a broad frequency range 100 megahertz (MHz) to 3000 gigahertz (GHz) (wavelength roughly ranging from 0.1 millimeter (mm) to 3 meter (m)) to heat and dissociate hydrocarbon gas hydrates, with microwave radiation stated as being preferred. Microwave radiation, which has a wavelength in the 0.1 mm to 1 mm range, is widely used to transfer energy to materials containing liquid water (e.g., as in a conventional microwave oven wherein food is heated by the resultant heating of the aqueous component of the food). In the case of a hydrate, sufficient microwave exposure can impart energy to the water molecules and cause the breaking of the hydrogen bonds of the water in the clathrate structure in addition to heating the water molecules.

[0075] Energy of a targeted wavelength may be applied to release a contained gas within a gas hydrate by electromagnetically inducing collective vibrational modes of the gas hydrate. In one embodiment, a method is provided for selectively releasing trapped gas molecules from their hydrate cages and harvesting the released gas molecules. The trapped gas in the gas hydrate may be methane or any other gas, including hyrocarbons. Sub-millimeter wavelength radiation in the 0.5 - 32 THz region of the electromagnetic spectrum may be applied to the gas hydrate. At least a portion of the trapped gas is released, via energy gap reduction associated with the clathrate hydrate and induced by the radiation. The released gas may then be harnessed as fuel energy.

[0076] In further detail, sub-millimeter radiation in the 0.5 - 32 THz region of the electromagnetic spectrum may be applied to methane or other trapped hydrocarbon gas hydrate to excite the large-amplitude gas-hydrate vibrations (i.e., instead of simply imparting heat energy directly to the water molecules). In one embodiment, this directly impacts the hydrogen-bonding between the water molecules in the hydrate. The vibrations induced by the electromagnetic radiation can cause the energy gap between the highest-energy occupied gas-hydrate bonding molecular orbitals (HOMOs) and lowest-energy, otherwise unoccupied gas- hydrate anti-bonding molecular orbitals (LUMOs) to close. This can result in the pouring of electrons from the bonding into the anti-bonding gas-hydrate orbitals, thereby causing the release of the gas from its water- clathrate cages. This vibronic process can be more efficient in releasing the gases from the clathrate structure than broad frequency microwave or other electromagnetic heating process.

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Spacecraft Propulsion

[0077] Gridded electrostatic ion thrusters for interplanetary and interstellar spacecraft propulsion typically utilize xenon gas as a source for ions. This gas has no charge and is ionized by bombarding it with energetic electrons. The electrons are provided from a hot cathode filament and accelerated in the electrical field between a cathode and an anode. In another embodiment, the electrons may be accelerated by the oscillating electric field induced by an alternating magnetic field of a coil, which results in a self-sustaining discharge (radiofrequency ion thruster). Positively charged water cluster ions, such as occurring naturally in water vapor or harvested from interstellar space (see W. W. Duley, Molecular Clusters in Interstellar Clouds, Astrophys. J. 471, L57, 1996), may be used instead of ionized xenon.

[0078] The positively charged water cluster ions are extracted by a system consisting of a plurality of multi-aperture grids. After entering the grid system via the plasma sheath, the cluster ions are accelerated due to the potential difference between the first and second grids. In some embodiments, the first grid is referred to as a screen and the second grid referred to as an accelerator grid. The water cluster ions can be accelerated to an ion energy of at least one keV, generating the thrust. This embodiment of an ion thruster emits a beam of positive charged water cluster ions. In order to avoid a charge-up of the spacecraft, a cathode placed near the engine emits additional electrons (the electron current is basically the same as the ion current) into the ion beam. This also prevents the beam of ions from returning to the spacecraft and thereby canceling the thrust. Therefore, neutral water clusters may also emitted can contribute to the thrust.

[0079] In another embodiment, negatively charged water clusters are harvested or generated and used in place of the positively charged water clusters. The system of multi-aperture grids are similarly used to extract and accelerate the negatively charged water clusters, by adjusting the potential differences between the grids. This embodiment of an ion thruster emits a beam of negatively charged water cluster ions. In order to avoid the charging-up of the spacecraft an anode may be placed near the engine. Therefore, neutral water clusters may also emitted can contribute to the thrust.

TERAHERTZ RADIATION TECHNOLOGIES Terahertz Radiation Generation

[0080] In modern terahertz sensing and imaging spectroscopy, water can, in some embodiments, be a barrier due to radiation absorption in the Terahertz frequency range. Water clusters, however can also be used in the generation of intense broadband Terahertz radiation. In one embodiment, a method for

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generating terahertz radiation includes applying a laser pulse to water clusters in water vapor. The laser pulse may be of any intensity necessary to activate the vibronic properties, notably the terahertz-frequency vibrations and the large electric dipole moments of water clusters of the water clusters. The water vapor may be contained in a gas cell or injected from a gas jet nozzle. The large oscillating electric dipole moments of water clusters present in the water vapor in either systems can significantly contribute to the generation of intense Terahertz radiation. The peak power levels and broadband frequency range of the Terahertz radiation generated from these systems can then be applied to non-linear spectroscopy, imagining, communications, and biomedical diagnostics and treatments.

Terahertz Frequency Communications

[0081] The term "Terahertz communications" can mean effective data rates exceeding 1 Terabit per second (usually on an optical carrier), or communication with a Terahertz carrier wave. Although greater bandwidths may be obtained at optical wavelengths with point-to-point optical communications, a number of reasons can make communications at Terahertz frequencies attractive. One reason may be the availability of the frequency band and the communications bandwidth. Frequencies above 300 GHz are currently unallocated by the Federal Commission. Terahertz communications is in the early stages of development, with first data transmission in this frequency range reported in the last few years. The disadvantages of communications at Terahertz frequencies arise through strong absorption through the atmosphere caused by water vapor as well as low efficiency and relatively low power available from currently available sources.

[0082] Water vapor can be a strong emitter of Terahertz radiation, as discussed in US Patent

Application 11/582,817. Since water vapor can be a strong emitter of Terahertz radiation due to the stimulation of water clusters' vibronic properties present in water vapor in the atmosphere, this property may be used to promote wireless communications both in land based and satellite systems. Terahertz radiation can be generated from water clusters present in the atmosphere and space and then tuned to specific frequencies that match up with the known "atmospheric windows" in the water vapor spectrum, around the 1.3 THz and 1.5 THz frequencies. The Terahertz radiation can be of varying intensity, and may be controlled, for example, by stimulation of water clusters' vibronic properties. Such terahertz frequencies do not suffer from strong absorption through the atmosphere and can be utilized to produce astronomical data from ground based Terahertz telescopes. These frequencies can also function as the carrier frequencies for communications signals over long distances.

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Advanced Defense Systems Design

[0083] The interaction between high-intensity, ultra-short laser pulses and water-cluster plasmas generated from water vapor can lead to an emission of intense, coherent, short-pulse radiation at terahertz frequencies (see Johnson et al, "Water Vapor: An Extraordinary Terahertz Wave Source Under Optical Excitation", Physics Letters A 372, 6037, 2008). A system and method of using short-pulse radiation at terahertz frequencies to deactivate an electronic system is disclosed. The system and method may be used to target an electronic system a substantial distance away. The system and method may be adapted to create a virtual shield for any advancing army, navy or air force. The delivery of the Terahertz radiation pulses may be silent, invisible, smokeless and odorless. The short pulse radiation may be used to destroy enemy weapon systems, command and control structures and bases. By adjusting the frequency of the Terahertz radiation, human beings may be unharmed.

[0084] An embodiment of such a defense system may be implemented to emit Terahertz radiation from any vantage point, such as from space satellites, from aircraft, or from a tower. Beaming the short- pulse radiation at terahertz frequencies from a vantage point can provide an electronic shield for or against an advancing army, airforce or navy. The electronic shield may create a zone within which electronic devices are disabled or partially disabled. The zone may also prevent enemy transport vehicles and projectiles to advance past the zone by disabling any electronic devices on board the vehicles or projectiles. In some embodiments, the vehicles or projectiles may not be fully disabled but enemy activities can be disrupted. Another embodiment of the same technology may be used to create distortions in the radar detection systems of an enemy. Application of the technology can be made possible from a distance away, based in part on relatively low atmospheric absorption described above. This application can also be adapted to counter- terrorism, for example, for use in the airport or other public areas. For example, using terahertz radiation pulses to disable electronic devices suspected to be involved in terror acts may be safer than conventional methods.

CHEMICAL SYNTHESIS AND REACTIVITY Oxidation Applications

[0085] The water clusters described in this patent can have highly reactive oxygen components.

These water clusters can be used in various methods, particularly in "oxidative" reactions (i.e. reactions that involve transfer of an oxygen from one molecule to another) though not limited to such reactions. The

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clusters can be employed in any oxidative reaction, including but not limited to the combustion applications mentioned in the clean energy production applications. The water clusters, in combination with any appropriate reaction partner, can increase chemical reaction rates and chemical synthesis. In some embodiments, a method of increasing reactive behavior in chemical reactions associated with water includes applying radiation, at a frequency in the range of 0.5 terahertz to 32 terahertz, to a plurality of water clusters in the chemical reaction. In other embodiments, other types of stimulus to activate the vibronic interactions of water clusters can also improve reactive behavior in chemical reactions.

Biocidal Applications

[0086] Negatively charged water clusters and water clusters clathrating biocatalytic elements such as silver (Ag) in the form of nano-sprays and nano-emulsions can exhibit biocidal activity. For example, they may kill pathogenic bacteria such as Staphylococcus, Streptococcus, Salmonella, E. CoIi, as well as the spore-forming bacterium. Bacillus Anthracis, responsible for Anthrax. A bicatalytic element can disable an enzyme of a bacteria, virus, fungi, or any other form and type of pathogenic agent. When clathrated by water clusters, the vibronic interactions helps to activate the bicatalytic element's catalytic interaction with the enzyme of a pathogenic agent, disabling the pathogenic agent.

[0087] These biocidal formulations may be delivered via various media and using various methods.

For example, an oil-based medium may be used to deliver a biocidal emulsion. The emulsion can be injected or directly applied to a mass afflicted with a bacteria for example. In one embodiment, nano-emulsions of silver-clathrated water clusters can be applied directly to the skin and function as an "over-the-counter" antiseptic.

[0088] In one embodiment, a method for imparting a biocidal property to a water-based spray or emulsion against a pathogenic agent includes applying at least one negatively-charged water cluster to a pathogenic agent. In another embodiment, a method for imparting a biocidal property against a pathogenic agent includes clathrating a bicatalytic element with a water cluster. The negatively-charged water cluster or clathrated bicatalytic element is then applied to the pathogenic agent to kill or disable the pathogenic agent. In one embodiment, the bicatalytic element is silver. The negatively-charged water cluster or clathrated bicatalytic element may be further stimulated by radiation to improve the biocidal activity.

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PHARMACEUTICAL & BIOMEDICAL TECHNOLOGIES Pharmaceutical Drug Development

[0089] Water cluster vibronic interactions may be used to design novel drugs that accelerate electron-transfer, proton transfer and chemical reactions. These vibronically active water clusters may be present within the body naturally or delivered in water vapor or water-in-oil nano-emulsions. Such water clusters can lower the energy barrier for the reactions along the cluster Terahertz-frequency vibrational modes. This method may be used in conjunction with stimulated Terahertz radiation to further enhance drug-biomolecule resonance. A method of delivering pharmaceuticals to diseased cells and bio-molecules includes using water-cluster micelles of the type shown schematically in FIG. 11. A micelle is an aggregate of surfactant molecules dispersed in a liquid colloid, in this case, water clusters. The unique THz-frequency vibrations of these water cluster (or nano-cluster) micelles can facilitate their resonance interaction with diseased cell and other biomolecules, including DNA and proteins. Stabilizing surfactants for the micelle can include fatty acid and alcohol ethoxylates.

Transdermal Delivery

[0090] The pharmaceutical industry has devoted a significant part of its resources towards the development of drugs that can be delivered transdermally to the bloodstream (through the stratum corneum and deeper skin layers) for the treatment of afflictions ranging from skin disorders to bodily disease. Transdermal drug delivery systems provide for the controlled release of drugs directly into the bloodstream through intact skin. Transdermal drug delivery can be an attractive alternative when oral drug treatment is not possible or desirable. In particular, with transdermal administration, therapeutic activity may be prolonged and controlled activity can be achieved.

[0091] First-principles quantum-chemical computations of the electronic structure and vibrational modes of water nano-clusters like the one, (H ₂ O) _2I H ⁺ shown in FIG. 7 suggests application of water clusters to transdermal delivery. Such permeating water clusters can (1) clathrate and deactivate lipid hydrophobes responsible for the stratum corneum hydration barrier, (2) thereby enable transdermal delivery of clathrated pharmaceuticals, (3) scavenge free radicals that damage epidermal cells and interfere with drug delivery, and (4) be subject to less water evaporation from the skin because of the intrinsic stabilities of the water nanoclusters.

[0092] Water clusters' vibration frequencies extend into the terahertz (THz) region of the electromagnetic spectrum, such as the 1.5 THz vibrational mode shown in FIG. 7 for the (H ₂ O) _2I H ⁺ cluster

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by the oxygen atomic displacement vectors. Water cluster "surface" Terahertz vibrational modes like the one above can be important because they couple or "resonate" with Terahertz-frequency vibrations of the amino- acid residues in epidermal proteins. Water in the form of small clusters is therefore not merely a solvent for epidermal proteins and other bio-molecules but helps to activate them through the resonant dynamics of the clustered water molecules at the skin cellular interfaces.

[0093] In U.S. Patents 5,800,576 and 5,997,590, and US Patent Application US2006/0110418, it was shown that small clusters of water molecules can be created in water-in-oil (W/O) nano-emulsions, providing a medium for delivering active water clusters to the skin to yield high epidermal permeability and improved delivery of water to within the outer layer of human skin. Pharmaceutical ingredients that can be transdermally delivered by nano-emulsions include FDA-approved transdermally deliverable "classic" drugs such as hormonally active testosterone, progesterone, and estradiol, glycyril trinitrate (e.g., for treatment of angina), hyoscine (e.g., for seasickness), nicotine (e.g., for smoking cessation); prostaglandin El (e.g., for treatment of erectile dysfunction); proteins and peptides; DNA and oligo-nucleotides (e.g., for gene therapy; DNA vaccines).

Water Cluster Micelles for Drug Delivery to the Brain

[0094] The problem of delivering pharmaceutical agents to targeted areas of the brain is a known challenge in the treatment of brain disorders. This is due to the blood-brain barrier, which prevents the efficient and effective delivery of many diagnostic and therapeutic agents. A method of delivering such agents across the blood-brain barrier includes using water-cluster micelles of the type shown schematically in FIG. 11. A micelle is an aggregate of surfactant molecules dispersed in a liquid colloid, in this case, water clusters. The unique THz-frequency vibrations of these water cluster (or nano-cluster) micelles can facilitate their penetration through the blood-brain barrier. Such micelles can deliver pharmaceuticals, such as antineoplastic drugs, to brain tumors and other disorders. Stabilizing surfactants for the micelles can include fatty acids and alcohol ethoxylates.

Biomedical Treatments

[0095] Many diseases are associated with the conformational "misfolding" of proteins. Water

"restructured" as water clusters, or "nano-clusters" can play a role in the proper folding of proteins. The "misfolding" of proteins, making them dysfunctional and disease-causing may be associated with the failure of water molecules to associate in clusters that properly interact with the protein amino-acid residues. The

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development of drugs to treat such diseases should therefore be focused on the restoration of water clustering at the protein interfaces.

[0096] Water clusters' vibration frequencies extend into the terahertz (THz) region of the electromagnetic spectrum, such as the 1.5 Terahertz vibrational mode shown in FIG. 7 for the cluster by the oxygen atomic displacement vectors. Water cluster "surface" Terahertz vibrational modes like the one shown in FIG. 7 can be important because they couple or "resonate" with Terahertz-frequency vibrations of the amino-acid residues in proteins. This property may be key to optimizing the delivery of drugs to and their interaction with drug-receptor sites, where Terahertz vibrations of water clusters clathrating the drug in our proprietary nano-emulsions may provide the resonance need to restore the interfacial water restructuring necessary for proper protein folding. Formation of hydrogen bonds between a drug molecule and a water molecule will polarize the latter, resulting in former hydrogen bonding to other water molecules and the formation of water clusters that play a key role in drug receptor identification. Even in the absence of hydrogen bonding, drug molecules may tend to cause water restructuring and the formation of cage-like structures, which implies that the drug molecule will have a "water signature".

[0097] Additionally, the application of intense 1.5 THz radiation externally (or internally via

"nanobots") to restructure water near cancerous tissue, which is known to harbor more "liquid-like" water, can possibly complement drug treatment. For example, skin or sub-coetaneous tumors may treated with an intense external Terahertz radiation source, alone or in combination with a water-in-oil nanoemulsion formulation to restructure the bulk water-like properties of cancerous tissue into vibronically active water clusters, restoring healthy cell and tissue functioning. Instead of an intense external Terahertz radiation source, other stimuli may be applied to promote the vibronic interactions of water clusters.

[0098] Having described certain embodiments of methods and systems for utilizing the vibronic interactions of water clusters, it will now become apparent to one of skill in the art that other embodiments incorporating the concepts of the disclosure may be used. Therefore, the disclosure should not be limited to certain embodiments, but rather should be limited only by the spirit and scope of the following claims.

4379139vl Attorney Docket No.: 2007135-0007 (HYDR)