Erratum: “Computing vibrational energy relaxation for high-frequency modes in condensed environments” [J. Chem. Phys. <b>107</b>, 10470 (1997)]

Articles you may be interested inOn the calculation of vibrational energy relaxation rate constants from centroid molecular dynamics simulations J. Chem. Phys. 119, 9030 (2003); 10.1063/1.1613636 High-frequency vibrational energy relaxation in liquids: The foundations of instantaneous-pair theory and some generalizationsA procedure is outlined to determine high-frequency spectra of classical liquids interacting via Lennard-Jones and similar potentials and applied to the problem of vibrational energy relaxation. The theory is based on analytical expressions derived for spherical particles in gases ͓Paper I, D. Schwarzer and M. Teubner, J. Chem. Phys. 116, 5680 ͑2002͔͒ and is extended to the dense liquid phase by considering binary collisions in the potential of mean force. The calculated spectra are in good agreement with those derived from classical trajectory and molecular dynamics simulations.

Section: Introductionsupporting

confidence: 89%

Vibrational energy relaxation in classical fluids. II. High-frequency spectra in liquids

Teubner

Schwarzer

2003

“…Q is a correction factor which relates the classical and quantum motions and ensures detailed balance. There has been much recent work on the appropriate value of Q, [38][39][40][41][42] but in our calculations it can be taken as being equal to one as the frequencies of the triiodide ion are low. This gives…”

Section: ͑16͒mentioning

confidence: 99%

Temperature and solvent dependence of vibrational relaxation of tri-iodide: A simulation study

Zhang

Lynden‐Bell

2003

“…For ground state vibrational transitions, a number of formulas have been derived which provide QCFs to classical vibrational energy relaxation results. 27,30,78,79 For low energy v = 10 transitions, the quantum correction factors are often small, (on the order of 2 -3) so long as one takes care to use reasonably accurate force fields. 27,78 Given that VER is notoriously sensitive to the system-bath coupling, it is therefore usually difficult to determine whether discrepancies between calculated VER and experimental VER in condensed phase systems arise from the QCF, or from errors in the potential.…”

Section: Anharmonic Pes and Dynamics Of The Df Morse Oscillatormentioning

confidence: 99%

Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD3CN treated with a parallel multi-state EVB model

Glowacki

Orr-Ewing

Harvey

2015

We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD3CN → DF + CD2CN reaction in CD3CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD3CN solvent, equilibrium power spectra of DF in CD3CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ∼23 kcal mol−1 localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD3CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of the post-reaction solvation environment results in a red shift. These two competing effects mean that the post-reaction relaxation profile is distinct from what is observed when Franck-Condon vibrational excitation of DF occurs within a microsolvation environment initially at equilibrium. Our conclusions, along with the theoretical and parallel software framework presented in this paper, should be more broadly applicable to a range of complex reactive systems.