Isotropic Raman line shapes of N2 and O2 along their liquid–gas coexistence lines

Everitt, K. F.; Skinner, James

doi:10.1063/1.1412248

Cited by 28 publications

(36 citation statements)

References 47 publications

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“…These quantities are important in studies of ͑pure͒ vibrational dephasing and vibrational relaxation. The mixed quantum-classical method presented here may be applied not only to study these problems but also spectroscopy 2,8,10,11,13 and reaction dynamics 34,35,[40][41][42] in condensed phase systems. A key advantage is the physical insight available from the QC trajectory consisting of solvent positions and momenta and the vibrational wave function as a function of time.…”

Section: Discussionmentioning

confidence: 99%

“…This approach has been widely and successfully used for weakly coupled solute-solvent systems. [9][10][11][12][13] A vibrationally adiabatic QC simulation directly provides the fluctuating frequencies of a quantum-mechanical solute from dynamics that include response from the quantum mode͑s͒ onto the classical coordinates. Further, an explicit calculation of the vibrational energy levels is accurate even for strong solute-solvent coupling, unlike perturbation theory approaches.…”

Section: Introductionmentioning

confidence: 99%

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A general method for implementing vibrationally adiabatic mixed quantum-classical simulations

Thompson

2003

The Journal of Chemical Physics

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An approach for carrying out vibrationally adiabatic mixed quantum-classical molecular dynamics simulations is presented. An appropriate integration scheme is described for the vibrationally adiabatic equations of motion of a diatomic solute in a monatomic solvent and an approach for calculating the adiabatic energy levels is presented. Specifically, an iterative Lanczos algorithm with full reorthogonalization is used to solve for the lowest few vibrational eigenvalues and eigenfunctions. The eigenfunctions at one time step in a mixed quantum-classical trajectory are used to initiate the Lanczos calculation at the next time step. The basis set size is reduced by using a potential-optimized discrete variable representation. As a demonstration the problem of a homonuclear diatomic molecule in a rare gas fluid (N 2 in Ar͒ has been treated. The approach is shown to be efficient and accurate. An important advantage of this approach is that it can be straightforwardly applied to polyatomic solutes that have multiple vibrational degrees-of-freedom that must be quantized.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A general method for implementing vibrationally adiabatic mixed quantum-classical simulations

Thompson

2003

The Journal of Chemical Physics

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“…Not many models for this part of the isotropic interaction depending of the vibration are available in the literature. For this kind of potential it is usual to consider site-site models which take into account the presence of the vibrational coordinate in the site-site distances, also it is assumed that the LennardJones parameters and σ present a linear dependence with the vibrational coordinate [5][6][7]. However, in this work, like in the previous one [8], we consider the model introduced by Marteau et al [9] for the binary isotropic interaction potential depending on the interaction.…”

Section: Interaction Potentials and Simulationsmentioning

confidence: 99%

“…The study of the fundamental and overtones infrared and Raman vibrational solvent shifts gives relevant information about the molecular interaction depending of the intramolecular vibration [1][2][3][4][5][6][7]. In an earlier work, according to Buckingham, it was deduced that the diatomic solvent shift associated to the vibrational transition 0 → ν of a cubic anharmonic oscillator presents a linear dependence with the vibrational quantum number ν [1].…”

Section: Introductionmentioning

confidence: 99%

A Simulation Study of the Fundamental Vibrational Shifts of HCl Diluted in Ar, Kr, and Xe: Anharmonic Corrections Effects

Padilla

Pérez

2012

International Journal of Spectroscopy

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We have calculated the vibrational solvent shifts of the fundamental bands of HCl diluted in Ar, Kr, and Xe solutions at different thermodynamic conditions by means of the molecular dynamics technique and a model for the isotropic part of the interaction depending on the vibration. The theoretical vibrational shifts, which were compared with the available experimental data, have been determined by considering both, the usual linear Buckingham terms and the nonlinear anharmonic corrections, and the latter omitted in a previous work for the HCl in Ar and Kr. We have found that the Buckingham contributions dominate the solvent shifts of the fundamental bands of HCl in Ar, Kr, and Xe, although the anharmonic shifts' present significant greater values than those obtained previously for N 2 diluted in liquid Ar and pure liquid N 2 , both at normal conditions. We have analyzed the solvent shifts influence of the linear and quadratic (in the vibrational coordinate) oscillator-bath interaction terms and also the Dunham intramolecular potential effects on the anharmonic contributions.

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“…The intermolecular potential energy is the sum of the following site-site (v ij ) between two molecules i and j [9]. The total intermolecular potential energy is taken to be…”

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confidence: 99%

Vibrational Phase Relaxation along the Critical Isochore of Nitrogen: The Role of Local Density Fluctuations in the Rate Enhancement

Roychowdhury

Bagchi

2003

Phys. Rev. Lett.

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Vibrational dephasing of the nitrogen molecule is known to show highly interesting anomalies near its gas-liquid critical point. Here we present theoretical and computational studies of the Raman linewidth of nitrogen along the critical isochore. The linewidth is found to have a lambda-shaped temperature dependence near the critical point. As observed in experimental studies, the calculated line shape becomes Gaussian as the critical temperature (T(c)) is approached. Both the present simulation and a mode coupling theory analysis show that the slow decay of the enhanced density fluctuations near the critical point, probed at the subpicosecond time scales by vibrational frequency modulation, along with an enhanced vibration-rotation coupling, are the main causes of the observed anomalies.

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Isotropic Raman line shapes of N2 and O2 along their liquid–gas coexistence lines

Cited by 28 publications

References 47 publications

A general method for implementing vibrationally adiabatic mixed quantum-classical simulations

A general method for implementing vibrationally adiabatic mixed quantum-classical simulations

A Simulation Study of the Fundamental Vibrational Shifts of HCl Diluted in Ar, Kr, and Xe: Anharmonic Corrections Effects

Vibrational Phase Relaxation along the Critical Isochore of Nitrogen: The Role of Local Density Fluctuations in the Rate Enhancement

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