EFTA02542944.pdf

From: Jeffrey Epstein <[email protected]> Sent: Sunday, September 4, 2011 6:32 PM To: Subject: Re: FW: A Quantum-Thermodynamic Ratchet For Photonic Frequency Up-Pumping? yes „ photosynthes is 8-90 % efficient. „ it acts becasue of the wave nat=re of light, this isthe next frontier. On Sun, Sep 4, 2011at 2:18 PM, «= href="mailto =ndation.org> wrote: That's true. How m=ny gaps do you think could be activated by one photon? =ust curious do you think that in our lifetimes we will have any energy bre=kthroughs? =p class="MsoNormal">From:=span style="font-size:10.0pt"> Jeffrey Epstein Imailto:[email protected]] Sent: Sunda Se tember 04, 2011 2:38 AM To: Subject: Re: FW: A Quantum-Thermodynamic Ratchet For Photonic F=equency Up-Pumping? =C24> photosynethes seems t= work by not needing the particle at all , but the reacting to its wave na=ure, . the light should be able to be tuned. and not one gap but man= being activated by the same photon On Sun, Sep 4, 2011at 2:48 AM, =It; <mailto > wrote: Oh Lord.=u> This is a v=ry hard problem — do you have any interesting inputs to add herek=span> =div> From:=span style="font-size:10.0pt"› Lowell Wood (mailto <mailto >1 S=nt: Saturday, September 03, 2011 11:38 PM To: Rod Hyde; Jordin Kare Cc: 'Nathan Myhrvold'; C=uck Whitmer - External; 'Jeff Bowers'; Boris Nikolic (BGC3); David =. Tuckerman; 'Casey Tegreene' Subject: A Quantum-Thermodynamic Ratchet For Photonic Frequency Up-P=mping? EFTA_R1_01694116 EFTA02542944  I continue to puzzle over BillQ=99s "cheaper-&-cleaner-&-more abundant electricity for eve=yone" challenge- to-Inventors — currently saided.=80, (entirely legally — physician's orders! J) by the modern version of the tradition=l opium-eater's favorite ingestible. 1 (Or. Nikolic admon=shes me to comply completely with "the doctor's orders4o=80. along these lines — which call for remarkably heavy-&-fr=quent dosings -- so please do blame him entirely for this missive! <=pan style="font-family:Wingdings">1) <1=> In order to generate the maximum voltag=-current product from a given area of (single-composition) semiconductor i=luminated with a given flux, it's clearly desirable to have monoch=omatic radiation that's 'matched' to the bandgap, =-&-p Fermi levels, etc. of the chosen semiconductor. Howev=r, what God gives us — in generous total quantities, if not pleasa=tly high fluxes :) -- is a —O.= eV Planckian spectrum with a batch of holes chewed in it, i.e., the solar=spectrum at AM1, for which the maximum-attainable energy conversion effici=ncy is widely believed to be 50.5. Even =hese performance levels are attained only with a half-dozen p-n junction a=tfully (i.e., very expensively) 'stacked' on each other, arch taking its bandgap-designated 'bite' from the incoming =adiation (and thus being semi- insanely expensive, even for USG purposes) =EN:* cf. appended Figure. It clearly would be greatly pref=rable to have a large fraction of the energy of the solar spectrum 4)=98presenteds to a suitable photovoltaic converter-assembly after b=ing 'transfigured' to single-energy (e.g., —2.5 eV) photon=. +++++=++++++++++++++++++++++ </=> So wh=t are the basic prospects for usefully — i.e., practically -- mono=hromatizing the AM1solar spectrum in the photovoltaic context?au> These=prospects would seem to be of non-trivial magnitudes — at least to=me-in-present condition! — as suggested by the appended items (whi=h 'connection' is admittedly somewhat distant)?au> Molec=lar quantum oscillators can have very high Qs in/about the visible optical=spectrum, e.g., 106, when they're in vacuum-type=circumstances, i.e., are 'natural linewidth'-constrained.=C2* However, these Qs can be depressed by as much as —4 orders-of-magnit=de, e.g., via collisional interactions in normal (zero-P, non-resonant) me=ia. 2 EFTA_R1_01694117 EFTA02542945  So, w=at can we do with sets-of-(preferably, high-Q molecular) oscillators Q=80Qphysically-&-spectrally associated' with each other in a =uitably engineered environment (seemingly likely enabled by contemporary l=thographic capabilities, which already offers minimum features sizes most =f an order-of-magnitude smaller than visible spectral wavelengths of inter=st)? We wo=ld presumably arrange these molecular assemblies in stacks of planar sheet= of 'unit cells' containing something of the order of a do=en high-oscillator strength transitions (perhaps carried on something like=a half-dozen well-chosen molecules — or quantum dots?) which would=together 'cover' the AM1 spectrum between, say, 0.5 and 1.= microns free-space wavelength. These=would serve to 'harvest' most all of the inputted so=ar radiation over this - 1.6 octave-width spectral band and then make it av=ilable for re-radiation by a 'master molecular' oscillator=located proximate to the 'unit cell' to whose upper-level =hey would each be (chosen to) be chosen to couple by short-range non-radia=ive energy transfer while concurrently making an 'energy contribut=on' of the order of a few kT to the local medium — so as t= helpfully make up energy differences between the two donating quantum osc=llators and the donated-to one and (not quite incidentally) to conf=r a degree of thermodynamic irreversibility onto the energy transfer proce=s. The d=nated-to molecule then fluoresces the up-pumped (in the frequency sense) q=antum energy with high quantum efficiency — helpfully conferred by=lack-of-competing de-excitations in its surroundings, e.g., the energy-goi=g- uphill inability to effectively back-transfer its excitation to adjacent=donating molecules. These=up-pumped, quasi-monochromatic photons are then 'inputted'=(via device-internal reflectors, etc. aimed at optical transfer efficiency=optimization) to a photovoltaic conversion section of the device. =U> Yes, of course I also have-in-mind the an=logous photochemical trick, in which we convert such 'spectrally- e=hanced sunlight' into high-energy chemical bond-rearrangements, e.=., energy efficiency-enhanced photosynthesis! +++++=++++++++++++++++++++ =u> Of present interest are two distinct item=: 3 EFTA_R1_01694118 EFTA02542946  [1] <=>Constructive (i.e., repair-oriented!) criticism-as-may-be-indicated o= the proposed physical mechanisms and stringing-togethers thereof; =u> (2] C=mments of a 'practical' or implementation-focused characte=, e.g., how can this proto-device be made to work significantly better 40=80* i.e., in-any-&-all-ways-more-practical -- than as-sketched above= 4,=A0 Thanks! Lowell</=> =/u> Artificial=light-harvesting method achieves 100% energy transfer efficiency =a href="http://www.physorg.com/archive/01-09-2011/" target="_blank">Se=tember 1, 2011 by Lisa Zyga <http://www.physorg.com/e=itorials/> By arranging porphyrin dye molecules on a clay surfa=e using the "Size-Matching Effect," researchers have demon=trated an energy transfer efficiency of approximately 100%, which is an im=ortant requirement for designing efficient artificial light-harvesting sys=ems. Image credit: Ishida, et al. ©2011 American Chemical Society<=u> (PhysOrg.com) In an attempt to mimic the photo=ynthetic systems found in plants and some bacteria, scientists have taken = step toward developing an artificial light-harvesting system (LHS) that m=ets one of the crucial requirements for such systems: an approximately 100= energy transfer efficiency. Although high energy transfer efficiency is j=st one component of the development of a useful artificial LHS, the achiev=ment could lead to clean solar- fuel technology that turns sunlight into ch=mical fuel. The researchers, led by Shinsuke Takagi from the Tok=o Metropolitan University and PRESTO of the Japan Science and Technology A=ency, have published their study on their work toward an artificial LHS in=a recent issue of the Journal of the American =hemical Society <http://www.physorg.com/tags/journal+of=the+american+chemical+society/> . 4 EFTA_R1_01694119 EFTA02542947  "In order to realize an artificial light-har=esting system, almost 100% efficiency is necessary," Takagi told <=>PhysOrg.com. "Since light-harvesting systems consist of many =teps of bacteria <http://www.physorg.com/tags/energy+transfer/> or plant leaves) is composed of regularly =rranged molecules that efficiently collect sunlight and carry the excitati=n energy to the system's reaction center. An artificial LHS (or =E24040artificial leaf") attempts to do the same thing by using f=nctional dye molecules. Building on the results of previous research, the sc=entists chose to use two types of porphyrin dye molecules for this purpose= which they arranged on a clay surface. The molecules' tendency to=aggregate or segregate on the clay surface made it challenging for the res=archers to arrange the molecules in a regular pattern like their natural c=unterparts. "A molecular arrangement with an appropriate=intermolecular distance is important to achieve nearly 100% energy transfe= efficiency," Takagi said. "If the intermolecular distance=is too near, other reactions such as electron transfer and/or photochemica= reactions would occur. If the intermolecular distance is too far, deactiv=tion of excited dye surpasses the energy transfer reaction." </=> In order to achieve the appropriate intermolecular d=stance, the scientists developed a novel preparation technique based on ma=ching the distances between the charged sites in the porphyrin molecules a=d the distances between negatively charged (anionic) sites on the clay sur=ace. This effect, which the researchers call the "Size-Matching Ru=e," helped to suppress the major factors that contributed to the p=rphyrin molecules' tendency to aggregate or segregate, and fixed t=e molecules in an appropriate uniform intermolecular distance. As Takagi e=plained, this strategy is significantly different than other attempts at a=hieving molecular patterns. "The methodology is unique," he said= "In the case of usual self-assembly systems, the arrangement is r=alized by guest-guest interactions. In our system, host-guest interactions=play a crucial role for realizing the special arrangement of dyes. Thus, b= changing the host material, it is possible to control the molecular arran=ement of dyes on the clay surface." As the researchers demonstrated, the regular arrange=ent of the molecules leads to an excited energy transfer efficiency <http://www.phys=rg.com/tags/transfer+efficiency/> molecules <http://=ww.physorg.com/tags/molecules/> and clay h=st materials look like promising candidates for an artificial LHS.<=> "At the present, our system includes only tw= dyes," Takagi said. "As the next step, the combination of=several dyes to adsorb all sunlight is necessary. One of the characteristi= points of our system is that it is easy to use several dyes at once. Thus= our system is a promising candidate for a real light-harvesting system th=t can use all sunlight <http://www.physorg.com/tags/sunlight/> . We believe that even photochemical reaction parts can=be combined on the same clay surface. If this system is realized and is co=bined with a photochemical reaction center, this system can be called an =E24 inorganic leaf.'" More information: Yohei Ishida, et al. fe=9CEfficient Excited Energy Transfer Reaction in Clay/Porphyrin Complex tow=rd an Artificial Light-Harvesting System." Journal of the Ameri=an Chemical Society. 0O1:10/1021/ja20442Su Article</=> Efficient Excite= Energy Transfer Reaction in Clay/Porphyrin Complex toward an Artificial L=ght-Harvesting System • Abstract <http://pubs.acs.org/doi/abs/10.1021/ja20442Su> • Full Text HTML <http://pubs.acs.org/doi/full/10.1021/ja204425u> 5 EFTA_R1_01694120 EFTA02542948  Hi-Res PDF=1854 KBJ <http://pubs.acs.org/doi/pdf/10.1021/ja20=425u> Japan Society for the Promotion of Science (DC1), Ichibancho, Chiyoda-ku, T=kyo 102-8471, Japan <http://pubs.acs.org/doi/pdfplus/10.1021/=a204425u> PRESTO (Precur=ory Research for Embryonic Science and Technology), Japan Science and Tech=ology Agency, 4-1-8 Honcho Kawaguchi, Saitama, Japan J. Am. Chem. Soc., Article ASAP=/p> DOI: 10.1021/ja204425u <= class="MsoNormal">Publication Date (Web): August 2, 2011<=p> Copyright © 2011 American Chemical Society</=> <mailto:[email protected]=jp> <http://cas.org/> Section:=/u> Radiat=on Chemistry, Photochemistry, and Photographic and Other Reprographic Proc=sses <http://pubs.acs.org/topic/reprographic> Abstract =u> The quantitative excited energy tr=nsfer reaction between cationic porphyrins on an anionic clay surface was =uccessfully achieved. The efficiency reached up to ca. 100% owing to the =E2**Size-Matching Rule" as described in the text. It was revea=ed that the important factors for the efficient energy transfer reaction a=e (i) suppression of the self-quenching between adjacent dyes, and (ii) su=pression of the segregated adsorption structure of two kinds of dyes on th= clay surface. By examining many different kinds of porphyrins, we found t=at tetrakis(1-methylpyridinium-3-yl) porphyrin (m-TMPyP) and tetrak=s(1-methylpyridinium-4-yl) porphyrin (p-TMPyP) are the suitable por=hyrins to accomplish a quantitative energy transfer reaction. These findin=s indicate that the clay/porphyrin complexes are promising and prospective=candidates to be used for construction of an efficient artificial light-ha=vesting system. 40=A0 The information contained in this communication is =onfidential, may be attorney-client privileged, may constitute inside i=formation, and is intended only for the use of the addressee. It is the property of 6 EFTA_R1_01694121 EFTA02542949 Jeffrey Epstein Unau=horized use, disclosure or copying of this communication or any part th=reof is strictly prohibited and may be unlawful. If you have received t=is communication in error, please notify us immediately by return e-mail or=by e-mail to [email protected] <mailto:[email protected]> , and destroy this communication and all copies t=ereof, including all attachments. copyright -all rights reserved =/div> The information contain=d in this communication is confidential, may be attorney-client privileged, may constitute inside i=formation, and is intended only for the use of the addressee. It is the=property of Jeffrey Epstein Unauthorized use, disclosure or copying=of this communication or any part thereof is strictly prohibited and may be unla=ful. If you have received this communication in error, please notify us=immediately by return e-mail or by e-mail to [email protected] <[email protected]> , and destroy this communication and all copies thereof, including all attachm=nts. copyright -all rights reserved 7 EFTA_R1_01694122 EFTA02542950