Computer simulations of the solvation dynamics of Coumarin 153 in dimethylsulfoxide

Martins, Lucimara R.; Skaf, Munir S.

doi:10.1016/s0009-2614(03)00159-3

Cited by 21 publications

(25 citation statements)

References 25 publications

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“…The important result for present purposes is that the equilibrium C g;G ( t ) was shown to be (surprisingly) a very good approximation for a significant fraction (∼2/3) of the nonequilibrium S ( t )’s decay for the modeled non-hydrogen-bonding polar solvent CH 3 Cl. Similar success of a Gaussian time dependence for S ( t ) was found by Maroncelli for acetonitrile (CH 3 CN) solvent, ,, and by other authors for other solvents. ,,, This success rather strongly supported the inertial perspective: the dominant effect is of the solvent molecules’ initial free streaming motion, changing their positions and thus the energy gap. However, as anticipated in ref .…”

Section: Theoretical Analysissupporting

confidence: 79%

“…It is important to stress for later reference that, accordingly, the Coulomb force figures neither in the initial distribution nor in the dynamics . The second approximation is that the equilibrium TCF’s short time dynamics can be approximated by a Gaussian in time, − ,,,, characterized by a ground state frequency ω g . ,, Here, the second line involves the inertial Liouville operator p ·∇ r , while the last line is the evaluation for the present Coulomb potential energy case, and β is ( k B T ) −1 .…”

Section: Theoretical Analysismentioning

confidence: 99%

“…It is important to stress for later reference that, accordingly, the Coulomb force figures neither in the initial distribution nor in the dynamics. 106 The second approximation is that the equilibrium TCF's short time dynamics can be approximated by a Gaussian in time, [12][13][14][15]90,91,96,97 characterized by a ground state frequency ω g . 13,17,29…”

Section: Fsf Solvation Dynamics Simulationsmentioning

confidence: 99%

“…For the present contribution, we will henceforth adopt the specific definitions that “inertial” means free streaming solvent dynamics determined by the initial momenta rather than by charge change-induced forces and/or torques (i.e., it is the initial unforced free streaming motion changing particle positions and thus the energy gap Δ E ), − , that “Gaussian” behavior refers specifically to initial Gaussian time dependence for nonequilibrium or (approximate) equilibrium measures of the solvation dynamics function S ( t ), − ,,,, (rather than more general issues of Gaussian statistics ,, ), and that “underdamped” means that the solvent motion depends critically upon forces and/or torques, typically exhibiting decaying oscillations, and is to be contrasted with “overdamped”.…”

Section: Introductionmentioning

confidence: 99%

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Solvation Dynamics in Water. 4. On the Initial Regime of Solvation Relaxation

Rey

Hynes

2020

J. Phys. Chem. B

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It is shown, by means of numerical and analytic work, that initial molecular momenta play little significant role in the initial fast solvation relaxation that follows electronic excitation of, and charge creation for, a standard model system of a solute in water. Instead, the nonequilibrium dynamics are predominantly described by non-inertial "steering" by the torques directly generated by the newly created charge distribution. It is this process that largely overcomes inertia, and drives the relaxation dynamics on a time scale of a few tens of femtoseconds in the key initial regime of the dynamics. These results are discussed in the context of commonly employed descriptions such as inertial, Gaussian, and underdamped dynamical behavior.

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Section: Theoretical Analysissupporting

confidence: 79%

Section: Theoretical Analysismentioning

confidence: 99%

Section: Fsf Solvation Dynamics Simulationsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Solvation Dynamics in Water. 4. On the Initial Regime of Solvation Relaxation

Rey

Hynes

2020

J. Phys. Chem. B

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“…As the computer simulation requires averaging over a large number of independent simulations and is therefore timeconsuming, only few studies focus solely on nonequilibrium simulation. [7][8][9][10] More often, nonequilibrium computational solvation dynamics is accompanied [11][12][13][14][15][16] or even replaced 4,[17][18][19][20][21][22][23][24][25] by equilibrium molecular dynamics simulation. Here, the nature of DUðtÞ is assumed to depend linearly on the perturbation, so that the nonequilibrium event can be described by the energy fluctuations present in the equilibrium state of the system.…”

Section: Introductionmentioning

confidence: 99%

On the validity of linear response approximations regarding the solvation dynamics of polyatomic solutes

Heid

Moser

Schröder

2017

Phys. Chem. Chem. Phys.

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The time-dependent fluorescence of a chromophore can be calculated from either nonequilibrium simulations, or, as long as linear response theory holds true, from equilibrium solvent fluctuations in the ground or excited state if the perturbation inflicted by the chromophore is small. The assumption of Gaussian statistics, in contrast, links the nonequilibrium dynamics to solvent fluctuations solely in the excited state, as long as the energy gap distribution is Gaussian throughout the process. The validity of linear response theories on the ground and excited state surface as well as Gaussian statistics is thoroughly tested in this study by calculating the time-dependent Stokes shift of different benzene-like solutes. The effect of the size of change in partial charges of the solute, the multipolar order of charge distribution, the direction of change, as well as the influence of different solvents on the validity of linear response theory is examined by simulating 54 different systems. Calculation of the Gaussian character of the energy distribution in equilibrium, as well as the time-evolution of the peak width in the nonequilibrium simulation sheds light on the validity of Gaussian statistics in a nonstationary regime. We observed that a large intermediate broadening of the width of the energy distribution correlates with a failure of correlation functions to describe the nonequilibrium event. These results are accompanied by analysis of higher order correlation functions, as well as the structure of the solvents water, acetonitrile and methanol around the solute, to yield a comprehensive view, as well as general guidelines, on when and why equilibrium solvent fluctuations can correctly depict solvation dynamics.

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The Chemical Environment of Ionic Liquids: Links Between Liquid Structure, Dynamics, and Solvation

Kobrak¹

2008

Advances in Chemical Physics

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Computer simulations of the solvation dynamics of Coumarin 153 in dimethylsulfoxide

Cited by 21 publications

References 25 publications

Solvation Dynamics in Water. 4. On the Initial Regime of Solvation Relaxation

Solvation Dynamics in Water. 4. On the Initial Regime of Solvation Relaxation

On the validity of linear response approximations regarding the solvation dynamics of polyatomic solutes

The Chemical Environment of Ionic Liquids: Links Between Liquid Structure, Dynamics, and Solvation

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