Vibrational relaxation of a dipolar molecule in water

Whitnell, Robert M.; Wilson, Kent R.; Hynes, James T.

doi:10.1063/1.462720

Cited by 209 publications

(175 citation statements)

References 63 publications

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“…This is the essence of the Landau-Teller formula for vibrational energy relaxation. 72,73 In our case, this statement means looking at the resonant In the latter case, very little spectral contribution is found since this frequency falls in between the bending and stretching peaks. However, we find that the window function is quite broad in both cases, and the whole vibrational spectrum contributes almost equally to the overall rate.…”

Section: F Quantized Correlation Functions and Quantum Transition Ramentioning

confidence: 70%

Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

Borgis

Rossky

Túri

2006

The Journal of Chemical Physics

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Abstract:A new, alternative form of the golden rule formula defining the non-adiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the non-adiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via MD simulations. The formalism is applied to the problem of the non-adiabatic s p → relaxation of an equilibrated pelectron in water and methanol. We find that, in both solvent, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated non-adiabatic coupling.d

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Section: F Quantized Correlation Functions and Quantum Transition Ramentioning

confidence: 70%

Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

Borgis

Rossky

Túri

2006

The Journal of Chemical Physics

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“…This equation is called the LTZ formula, which has been applied to the study of VER in liquids (21). This strategy was used by Sagnella and J.E.S.…”

Section: Theoriesmentioning

confidence: 99%

Vibrational energy relaxation in proteins

Fujisaki

Straub

2005

Proc. Natl. Acad. Sci. U.S.A.

121

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An overview of theories related to vibrational energy relaxation (VER) in proteins is presented. VER of a selected mode in cytochrome c is studied by using two theoretical approaches. One approach is the equilibrium simulation approach with quantum correction factors, and the other is the reduced model approach, which describes the protein as an ensemble of normal modes interacting through nonlinear coupling elements. Both methods result in similar estimates of the VER time (subpicoseconds) for a CD stretching mode in the protein at room temperature. The theoretical predictions are in accord with previous experimental data. A perspective on directions for the detailed study of time scales and mechanisms of VER in proteins is presented.W hen a protein is excited by ligand binding, ATP attachment, or laser pulses, vibrational energy relaxation (VER) occurs. Energy initially ''injected'' into a localized region flows to the rest of the protein and surrounding solvent. VER in large molecules (including proteins) is an important problem for chemical physics (1,2). Even more significant is the challenge to relate VER to fundamental reaction processes, such as a conformational change or electron transfer of a protein, associated with protein functions. The development of an accurate understanding of VER in proteins is an essential step toward the goal of controlling protein dynamics (3).Because of the advance of laser technology, there have been many experimental studies of VER in proteins (4-17). These experimental works are impressive, but it is difficult to derive detailed information from the experimental data alone. Theoretical approaches, including atomic-scale simulations, can provide more detailed information. In turn, experimental data can be used to refine simulation methods and empirical force fields. This combination of experimental and theoretical studies of protein structures and dynamics has begun to blossom. As experimental methods develop further and theoretical approaches grow in accuracy, the relationship will become fruitful.There have been many theoretical tools (see Theories) developed to analyze VER in proteins. Some aspects of VER in proteins can be explained by perturbative formulas based on the equilibrium condition of the bath (see Cyt c), but the use of the perturbative formulas may be too restrictive to describe protein dynamics generally at room temperature. In this article, we not only discuss the success of such established methods but also present a perspective on the study of VER in proteins. TheoriesIn this section, we present a selective overview of theories appropriate for the study of VER in proteins. For the most part, these theories have been developed to deal with VER in liquids, solids, or glasses. For recent reviews, see refs. 18-20. We refer to two distinct categories; one is based on equilibrium dynamics and Fermi's golden rule, whereas the other is based on nonequilibrium dynamical models.Fermi's Golden Rule. If (i) there is a clear separation between the system and bath, (...

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“…Comparison of the associated power spectrum with the known spectroscopic features of the solvent has sometimes served to qualitatively identify the solvent motions involved; the situation here is analogous to that for tcf studies of vibrational energy transfer, where similar comparisons implicate e.g. which solvent modes are energy receptors without directly observing the solvent molecules receiving the energy [42][43][44][45] . It is to be noted that, besides its qualitative character, this tcf approach suffers from additional limitations.…”

Section: Introductionmentioning

confidence: 98%

Solvation Dynamics in Liquid Water. 1. Ultrafast Energy Fluxes

Rey

Hynes

2015

J. Phys. Chem. B

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Solvation dynamics in liquid water is addressed via nonequilibrium energy transfer pathways activated after a neutral atomic solute acquires a unit charge, either positive or negative. It is shown that the well-known nonequilibrium frequency shift relaxation function can be expressed in a novel fashion in terms of energy fluxes, providing a clearcut and quantitative account of the processes involved. Roughly half of the initial excess energy is transferred into hindered rotations of first hydration shell water molecules, i.e. librational motions, specifically those rotations around the lowest moment of inertia principal axis. After integration over all water solvent molecules, rotations account for roughly 80 % of the energy transferred, while translations have a secondary role; transfer to intramolecular water stretch and bend vibrations is negligible. This picture is similar to that for relaxation of a single vibrationally or rotationally excited water molecule in neat liquid water, although solvation relaxation is more non-local. In addition, we find a remarkable independence of the main relaxation channels on the newly created charges sign. Although the methodology is applied here to the simplest solute case, the approach is rather general, and it should be at least equally useful in more realistic and complex scenarios.

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Vibrational relaxation of a dipolar molecule in water

Cited by 209 publications

References 63 publications

Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

Vibrational energy relaxation in proteins

Solvation Dynamics in Liquid Water. 1. Ultrafast Energy Fluxes

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