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Register a new userIsoenergetic Two-Photon Excitation Enhances Solvent-to-Solute Excited-State Proton Transfer
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Two-photon excitation is an attractive means for controlling chemistry in both space and time. Isoenergetic one- and two-photon excitations (OPE and TPE) in non-centrosymmetric molecules are often assumed to reach the same excited state and, hence, to produce similar excited-state reactivity. We compare the solvent-to-solute excited-state proton transfer of the super photobase FR0-SB following isoenergetic OPE and TPE. We find up to 62 % increased reactivity following TPE compared to OPE. From steady-state spectroscopy, we rule out the involvement of different excited states and find that OPE and TPE spectra are identical in non-polar solvents but not in polar ones. We propose that differences in the matrix elements that contribute to the two-photon absorption cross sections lead to the observed enhanced isoenergetic reactivity, consistent with the predictions of our high-level coupled-cluster-based computational protocol. We find that polar solvent configurations favor greater dipole moment change between ground and excited states, which enters the probability for two-photon excitations as the absolute value squared. This, in turn, causes a difference in the Franck-Condon region reached via TPE compared to OPE. We conclude that a new method has been found for controlling chemical reactivity via the matrix elements that affect two-photon cross sections, which may be of great utility for spatial and temporal precision chemistry.
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Selectively exciting target molecules to high vibrational states is inefficient in the liquid phase, which restricts the use of IR pumping to catalyze ground-state chemical reactions. Here, we demonstrate that this inefficiency can be largely solved by confining the liquid in an optical cavity under vibrational strong coupling conditions. For a liquid solution of $^{13}$CO$_2$ solute in a $^{12}$CO$_2$ solvent, cavity molecular dynamics simulations show that exciting a polariton (hybrid light-matter state) of the solvent with an intense laser pulse, under suitable resonant conditions, may lead to a very strong (> 3 quanta) and ultrafast (< 1 ps) excitation of the solute, all while the solvent is barely excited. By contrast, outside a cavity the same input pulse fluence can excite the solute by only half a vibrational quantum and the selectivity of excitation is low. Our finding is robust under different cavity volumes, which may lead to observable cavity enhancement on IR photochemical reactions in Fabry-Perot cavities.
We have investigated photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)$_4$(2,2-bipyridine)]$^{2-}$ (1), [Fe(CN)$_4$(2,3-bis(2-pyridyl)pyrazine)]$^{2-}$ (2) and [Fe(CN)$_4$(2,2-bipyrimidine)]$^{2-}$ (3) complexes in various solvents with static and time-resolved UV-visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering. We observe $^3$MLCT lifetimes from 180 fs to 67 ps over a wide range of MLCT energies in different solvents by utilizing the strong solvatochromism of the complexes. Intramolecular electron transfer lifetimes governing $^3$MLCT relaxation increase monotonically and (super)exponentially as the $^3$MLCT energy is decreased in 1 and 2 by changing the solvent. This behavior can be described with non-adiabatic classical Marcus electron transfer dynamics along the indirect $^3$MLCT->$^3$MC pathway, where the $^3$MC is the lowest energy metal-centered (MC) excited state. In contrast, the $^3$MLCT lifetime in 3 changes non-monotonically and exhibits a maximum. This qualitatively different behaviour results from direct electron transfer from the $^3$MLCT to the electronic ground state (GS). This pathway involves nuclear tunnelling for the high-frequency polypyridyl skeleton mode ($hbaromega$ = 1530 cm$^{-1}$), which is more displaced for 3 than for either 1 or 2, therefore making the direct pathway significantly more efficient in 3. To our knowledge, this is the first observation of an efficient $^3$MLCT->GS relaxation pathway in an Fe polypyridyl complex. Our study suggests that further extending the MLCT state lifetime requires (1) lowering the $^3$MLCT state energy with respect to the $^3$MC state and (2) suppressing the intramolecular distortion of the electron-accepting ligand in the $^3$MLCT excited state to suppress the rate of direct $^3$MLCT->GS electron transfer.
Excited state electron and hole transfer underpin fundamental steps in processes such as exciton dissociation at photovoltaic heterojunctions, photoinduced charge transfer at electrodes, and electron transfer in photosynthetic reaction centers. Diabatic states corresponding to charge or excitation localized species, such as locally excited and charge transfer states, provide a physically intuitive framework to simulate and understand these processes. However, obtaining accurate diabatic states and their couplings from adiabatic electronic states generally leads to inaccurate results when combined with low-tier electronic structure methods, such as time dependent density functional theory (TDDFT), and exorbitant computational cost when combined with high-level wavefunction-based methods. Here we introduce a DFT-based diabatization scheme, {Delta}-ALMO(MSDFT2), which directly constructs the diabatic states using absolutely localized molecular orbitals (ALMOs). We demonstrate that our method, which combines ALMO calculations with the {Delta}SCF technique to construct electronically excited diabatic states and obtains their couplings with charge-transfer states using our MSDFT2 scheme, gives accurate results for excited state electron and hole transfer in both charged and uncharged systems that underlie DNA repair, charge separation in donor-acceptor dyads, chromophore-to-solvent electron transfer, and singlet fission. This framework for the accurate and efficient construction of excited state diabats and evaluation of their couplings directly from DFT thus offers a route to simulate and elucidate photoinduced electron and hole transfer in large disordered systems, such as those encountered in the condensed phase.
The four-electron oxygen reduction reaction on Pt catalyst in alkaline solution undergoes proton transfer via tunneling mechanism. The hydrogen/deuterium kinetic isotopic rate constant ratio (kH/kD ) = 32 in a low overpotential region, indicating the importance of the quantum-proton-tunneling at the rate-determining step (RDS). However, kH/kD goes down to 3 in a high overpotential region, suggesting the classical proton-transfer (PT) scheme. Therefore, there is a quantum-to-classical transition of PT process as a function of potential, which is confirmed by theoretical study.
Hybrid entangled states, having entanglement between different degrees-of-freedom (DoF) of a particle pair, are of great interest for quantum information science and communication protocols. Among different DoFs, the hybrid entangled states encoded with polarization and orbital angular momentum (OAM) allow the generation of qubit-qudit entangled states, macroscopic entanglement with very high quanta of OAM and improvement in angular resolution in remote sensing. Till date, such hybrid entangled states are generated by using a high-fidelity polarization entangled state and subsequent imprinting of chosen amount of OAM using suitable mode converters such as spatial light modulator in complicated experimental schemes. Given that the entangled sources have feeble number of photons, loss of photons during imprinting of OAM using diffractive optical elements limits the use of such hybrid state for practical applications. Here we report, on a simple experimental scheme to generate hybrid entangled state in polarization and OAM through direct transfer of classical non-separable state of the pump beam in parametric down conversion process. As a proof of principle, using local non-separable pump state of OAM mode l=3, we have produced quantum hybrid entangled state with entanglement witness parameter of W-1.25 violating by 8 standard deviation. The generic scheme can be used to produce hybrid entangled state between two photons differing by any quantum number through proper choice of non-separable state of the pump beam.
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