Solvent Mode Participation in the Nonradiative Relaxation of the Hydrated Electron

Prezhdo, Oleg V.; Rossky, Peter J.

doi:10.1021/jp9611232

Cited by 93 publications

(103 citation statements)

References 58 publications

(139 reference statements)

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“…͑A2͔͒, but the rapid stabilization of the occupied excited state is the opposite of what is seen in the other examples of nonadiabatic dynamics in water. 8,9,11,14,15 The origin of this reversal can be seen in Fig. 4.…”

Section: B Nonadiabatic Relaxation Of Excited Dielectronsmentioning

confidence: 89%

“…This is because nonadiabatic dynamics requires the full many-electron wave function for both the ground and excited states. Thus, condensed phase systems studied with nonadiabatic dynamics, such as solvated electrons, [8][9][10][11] proton transfer, 12,13 charge-transfer-tosolvent ͑CTTS͒, 14 -16 and donor-acceptor electron transfer complexes, 17 typically are simulated with only a single quan-tum degree of freedom. 18 This restriction to a single quantum degree of freedom is unfortunate because there are several hints that one-electron treatments do not always properly describe the electronic structure of solvated systems.…”

Section: Introductionmentioning

confidence: 99%

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Efficient real-space configuration-interaction method for the simulation of multielectron mixed quantum and classical nonadiabatic molecular dynamics in the condensed phase

Larsen

Schwartz

2003

The Journal of Chemical Physics

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We introduce an efficient configuration interaction ͑CI͒ method for the calculation of mixed quantum and classical nonadiabatic molecular dynamics for multiple electrons. For any given realization of the classical degrees of freedom ͑e.g., a solvent͒, the method uses a novel real-space quadrature to efficiently compute the Coulomb and exchange interactions between electrons. We also introduce an approximation whereby the classical molecular dynamics is propagated for several time steps on electronic potential energy surfaces generated using only a particularly important subset of the CI basis states. By only updating the important-states subset periodically, we achieve significant reductions in the computational cost of solving the multielectron quantum problem. We test the real-space quadrature for the cases of two electrons confined in a cubic box with infinitely repulsive walls and two electrons dissolved in liquid water that occupy a single cavity, so-called hydrated dielectrons. We then demonstrate how to perform mixed quantum and classical nonadiabatic dynamics by combining these computational techniques with the mean-field with surface hopping algorithm of Prezhdo and Rossky ͓J. Chem. Phys. 107, 825 ͑1997͔͒. Finally, we illustrate the practicality of the approach to multielectron nonadiabatic dynamics by examining the nonadiabatic relaxation dynamics of both spin singlet and spin triplet hydrated dielectrons following excitation from the ground to the first excited state.

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Section: B Nonadiabatic Relaxation Of Excited Dielectronsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Efficient real-space configuration-interaction method for the simulation of multielectron mixed quantum and classical nonadiabatic molecular dynamics in the condensed phase

Larsen

Schwartz

2003

The Journal of Chemical Physics

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“…A number of quantum and semiclassical approaches have been developed for the description of transfer dynamics in large systems [48][49][50][51][52][53][54]. Mixed quantum-classical molecular dynamics, in which a few quantum mechanical electronic or vibrational modes are coupled to many explicit classical degrees of freedom, are used for modeling of transfer reactions, which produce substantial differences in the electrostatic interactions in the donor and acceptor configurations and generate large solvation and reorganization energies [55][56][57][58][59][60][61].…”

Section: E-mail Address: Prezhdo@uwashingtonedu (Ov Prezhdo)mentioning

confidence: 99%

Ab initio study of exciton transfer dynamics from a core–shell semiconductor quantum dot to a porphyrin-sensitizer

Kilin

Tsemekhman

Prezhdo

et al. 2007

Journal of Photochemistry and Photobiology A: Chemistry

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The observed resonance energy transfer in nanoassemblies of CdSe/ZnS quantum dots and pyridyl-substituted free-base porphyrin molecules [Zenkevich et al., J. Phys. Chem. B 109 (2005) 8679] is studied computationally by ab initio electronic structure and quantum dynamics approaches. The system harvests light in a broad energy range and can transfer the excitation from the dot through the porphyrin to oxygen, generating singlet oxygen for medical applications. The geometric structure, electronic energies, and transition dipole moments are derived by density functional theory and are utilized for calculating the Förster coupling between the excitons residing on the quantum dot and the porphyrin. The direction and rate of the irreversible exciton transfer is determined by the initial photoexcitation of the dot, the dot-porphyrin coupling and the interaction to the electronic subsystem with the vibrational environment. The simulated electronic structure and dynamics are in good agreement with the experimental data and provide real-time atomistic details of the energy transfer mechanism.

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“…Although the instantaneous normal mode (INM) treatment of the solvated electron system has been developed successfully, 49 for the present work we use the simpler atomistic Cartesian coordinate system (CC, only applicable in the high temperature limit) and a single molecule-based normal coordinate system (quasi normal modes, QNM) similar in philosophy to that of Prezhdo and Rossky. 50 The computational details of QNMs and the assignment of the frequencies are given in the next section. We will demonstrate below that the decoherence function is insensitive to the choice of coordinate system for our model.…”

Section: Ii1 the Decoherence Function In The Fg Formalismmentioning

confidence: 99%

Critical evaluation of approximate quantum decoherence rates for an electronic transition in methanol solution

Túri

Rossky

2004

The Journal of Chemical Physics

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We present a quantum molecular dynamics calculation of a semiclassical decoherence function to evaluate the accuracy of alternative short-time approximations for coherence loss in the dynamics of condensed phase electronically non-adiabatic processes. The semiclassical function from mixed quantum-classical molecular dynamics simulations and frozen Gaussian wave packets is computed for the electronic transition of an excited state excess electron to the ground state in liquid methanol. The decoherence function decays on a 10 fs timescale qualitatively similar to the aqueous case. We demonstrate that it is the motion of the hydrogen atom, and in particular, the hydrogen rotation around the oxygen-methyl bond which is predominantly responsible for destroying the quantum correlations between alternative states. Multiple timescales due to the slower diffusive a e-mail: turi@para.chem.elte.hu b e-mail: rossky@mail.utexas.edu 3 nuclear modes, which dominate the solvation response of methanol, do not contribute to the coherence loss. The choice of the coordinate representation is investigated in detail and concluded to be irrelevant to the decay. Changes in both nuclear momenta and positions on the two alternative potential surfaces are found to contribute to decoherence, the former dominating at short times (t < 5 fs), the latter controlling the decay at longer times. Various short-time approximations to the full dynamics for the decoherence function are tested for the first time. The present treatment rigorously develops the shorttime description and establishes its range of validity. Whereas the lowest-order short-time approximation proves to be a very good approximation up to about 5 fs, we also find that it bounds the decay of the decoherence function. After 5 fs, the coherence decay in fact becomes faster than the single Gaussian predicted in the lowest-order short-time limit.This decay is well reflected by an enhanced low-order approximation, which is also easily computed from equilibrium classical forces. 4

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Solvent Mode Participation in the Nonradiative Relaxation of the Hydrated Electron

Cited by 93 publications

References 58 publications

Efficient real-space configuration-interaction method for the simulation of multielectron mixed quantum and classical nonadiabatic molecular dynamics in the condensed phase

Efficient real-space configuration-interaction method for the simulation of multielectron mixed quantum and classical nonadiabatic molecular dynamics in the condensed phase

Ab initio study of exciton transfer dynamics from a core–shell semiconductor quantum dot to a porphyrin-sensitizer

Critical evaluation of approximate quantum decoherence rates for an electronic transition in methanol solution

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