The simultaneous, concerted transfer of electrons and protonselectron-proton transfer (EPT)-is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4′-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H þ is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck-Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated þ H─B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state.electron transfer | proton-coupled electron transfer P roton-coupled electron transfer (PCET), in which electrons and protons are both transferred, is at the heart of many energy conversion processes in chemistry and biology (1-6). PCET reactions can occur by sequential two-step transfers (e.g., electron transfer followed by proton transfer, ET-PT, or proton transfer followed by electron transfer, PT-ET) or by concerted electron-proton transfer (EPT) (1, 2). EPT pathways are important in avoiding high-energy intermediates, playing an integral role in photosynthesis and respiration, for example.Photo-driven EPT (photo-EPT), with electron and proton transfers occurring simultaneously during the optical excitation process, would appear to be ruled out on fundamental grounds, because electronic excitation occurs rapidly on the time scale for nuclear motions, including proton transfer. Using a combination of femtosecond pump-probe and coherent Raman techniques, we have observed simultaneous electron-proton transfer induced by intramolecular charge transfer (ICT) excitation in two different hydrogen-bonded adducts formed between an organic dye (A─O─H) and an external base (:B). One is formed between a para-nitrophenyl-phenol and an amine base, and the other between a coumarin derivative and an imidazole base (Fig. 1).The shift in electron density away from the hydroxyl group to the intramolecular ...
We consider states of the D1-D5 CFT where only the left-moving sector is excited. As we deform away from the orbifold point, some of these states will remain BPS while others can 'lift'. We compute this lifting for a particular family of D1-D5-P states, at second order in the deformation off the orbifold point. We note that the maximally twisted sector of the CFT is special: the covering surface appearing in the correlator can only be genus one while for other sectors there is always a genus zero contribution. We use the results to argue that fuzzball configurations should be studied for the full class including both extremal and near-extremal states; many extremal configurations may be best seen as special limits of near extremal configurations.
The D1D5 CFT gives a holographic dual description of a near-extremal black hole in string theory. The interaction in this theory is given by a marginal deformation operator, which is composed of supercharges acting on a twist operator. The twist operator links together different copies of a free CFT. We study the effect of this deformation operator when it links together CFT copies with winding numbers M and N to produce a copy with winding M +N , populated with excitations of a particular form. We compute the effect of the deformation operator in the full supersymmetric theory, firstly on a RamondRamond ground state and secondly on states with an initial bosonic or fermionic excitation. Our results generalize recent work which studied only the bosonic sector of the CFT. Our findings are a step towards understanding thermalization in the D1D5 CFT, which is related to black hole formation and evaporation in the bulk.
The D1D5 CFT has been very useful in the study of black holes. The interaction in this theory involves a twist operator, which links together different copies of a free CFT. For the bosonic fields, we examine the action of this twist when it links together CFT copies with winding numbers M and N to produce a copy with winding M + N . Starting with the vacuum state generates a squeezed state, which we compute. Starting with an initial excitation on one of the copies gives a linear combination of excitations on the final state, which we also compute. These results generalize earlier computations where these quantities were computed for the special case M = N = 1. Our results should help in understanding the thermalization process in the D1D5 CFT, which gives the dual of black hole formation in the bulk.
Excited-state proton-transfer dynamics between 7-hydroxy-4-(trifluoromethyl)coumarin and 1-methylimidazole base in toluene were studied using ultrafast pump-probe and time-resolved emission methods. Charge-transfer excitation of the hydroxycoumarin shifts electron density from the hydroxyl group to the carbonyl, resulting in an excited state where proton transfer to the base is highly favored. In addition to its the photoacid characteristics, the shift in the hydroxycoumarin electronic distribution gives it characteristics of a photobase as well. The result is a tautomerization process occurring on the picosecond time scale in which the 1-methylimidazole base acts as a proton-transfer shuttle from the hydroxyl group to the carbonyl.
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