Vibrational Population Relaxation in Liquids

Oxtoby, David W.

doi:10.1002/9780470142660.ch14

Cited by 280 publications

(77 citation statements)

References 87 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 98%

Solvation Dynamics in Liquid Water. 1. Ultrafast Energy Fluxes

Rey

Hynes

2015

J. Phys. Chem. B

View full text Add to dashboard Cite

show abstract

“…Here the transition rates k if from a vibrational state i to a state f are expressed in terms of matrix elements of the solute normal coordinates and classical TCF of the corresponding normal forces multiplied by a QCF. 53 The matrix elements were computed quantum mechanically, while the TCFs of forces were obtained from a classical MD calculation. The RH and LS approaches differ in many details, among others in the QCF whose specific form is ambiguous ͑see reviews 20,54 for extensive compari-son͒.…”

Section: Discussionmentioning

confidence: 99%

Nonequilibrium molecular dynamics simulations of vibrational energy relaxation of HOD in D2O

Kandratsenka

Schroeder

Schwarzer

et al. 2009

The Journal of Chemical Physics

View full text Add to dashboard Cite

Vibrational energy relaxation of HOD in deuterated water is investigated performing classical nonequilibrium molecular dynamics simulations. A flexible SPC/E model is employed to describe the intermolecular interactions and the intramolecular potential of the D(2)O solvent. A more accurate intramolecular potential is used for HOD. Our results for the OH stretch, OD stretch, and HOD bend vibrational relaxation times are 2.7, 0.9, and 0.57 ps, respectively. Exciting the OH stretching mode the main relaxation pathway involves a transition to the bending vibration. These results are in agreement with recent semiclassical Landau-Teller calculations. Contrary to this previous work, however, we observe a strong coupling of bending and OH stretching mode to the HOD rotation. As a result almost half of the total vibrational energy is transferred through the HOD rotation to the bath. At the same time the most efficient acceptor mode is the D(2)O rotation indicating the importance of resonant libration-to-libration energy transfer. We also find significant vibrational excitation of the D(2)O bending mode of the D(2)O solvent by V-V energy transfer from the HOD bending mode.

show abstract

“…Taking into account the quantum nature of nuclear motion by the method of Oxtoby [27], we can write P(e) as follows [21] PðeÞ…”

Section: Theorymentioning

confidence: 99%

Temperature dependence of the inelastic electron tunneling

Nishioka

Yamato

Kakitani

2006

Molecular Simulation

View full text Add to dashboard Cite

The property of the anomalous inverted region in the energy gap law which was found in the recent non-Condon theory of the electron transfer (ET) in protein media is investigated in more detail in relation to the inelastic electron tunneling. The physical aspect of the inelastic electron tunneling is theoretically discussed and schematically explained. Since it was previously shown that the inelastic electron tunneling mechanism worked significantly due to an exponential-like decay of the autocorrelation function of the electron tunneling matrix element with a small correlation time at 300 K, we investigated whether the similar exponential-like decay of the autocorrelation function is obtained or not and how the correlation time is changed at low temperatures. For this purpose, numerical calculations for the electron tunneling matrix element in the ET at 77 K from bacteriopheophytin (Bph) anion to the primary quinone in the reaction center of photosynthetic bacteria Rhodobacter sphaeroides are made. The results are that almost exponential-like decay of the autocorrelation function was obtained even at 77 K and the half decay time was of the similar magnitude to that at 300 K. Physical meaning of this temperature dependence is discussed.

show abstract

Vibrational Population Relaxation in Liquids

Cited by 280 publications

References 87 publications

Solvation Dynamics in Liquid Water. 1. Ultrafast Energy Fluxes

Solvation Dynamics in Liquid Water. 1. Ultrafast Energy Fluxes

Nonequilibrium molecular dynamics simulations of vibrational energy relaxation of HOD in D2O

Temperature dependence of the inelastic electron tunneling

Contact Info

Product

Resources

About