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Vibrational relaxation and decoherence in structured environments: a numerical investigation

Bonfanti, M. and Hughes, K.H. and Burghardt, I. and Martinazzo, R. (2015) Vibrational relaxation and decoherence in structured environments: a numerical investigation. Annalen der Physik. DOI: 10.1002/andp.201500144

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Abstract

Vibrational relaxation is a key issue in chemical reaction dynamics in condensed phase and at the gas-surface interface, where the environment is typically highly structured and cannot be expressed in terms of a simple friction coefficient. Rather, full knowledge of the coupling of the molecular oscillator to the environment is required, as typically subsumed in the spectral density of the environmental coupling. Here, we focus on harmonic Brownian motion and investigate the effectiveness of classical, canonical position autocorrelation functions to compute the spectral density of the coupling needed to describe vibrational relaxation in complex environments. Classical dynamics is performed on model systems, and several effects are investigated in detail, notably the presence of anharmonicity, the role of a high-frequency �Debye� cutoff in the environment and the influence of the detailed structure of the latter. The spectral densities are then used in standard independent oscillator Hamiltonian models which are numerically solved at T = 0 K to investigate quantum relaxation and decoherence

Item Type: Article
Subjects: Research Publications
Departments: College of Physical and Applied Sciences > School of Chemistry
Date Deposited: 09 Jul 2015 02:43
Last Modified: 03 Jul 2016 02:33
ISSN: 1521-3889
Publisher's Statement: This is the pre-peer reviewed version of the following article: Bonfanti, M., Hughes, K. H., Burghardt, I. and Martinazzo, R. (2015), Vibrational relaxation and decoherence in structured environments: a numerical investigation. Ann. Phys., which has been published in final form at http://dx.doi.org/10.1002/andp.201500144
URI: http://e.bangor.ac.uk/id/eprint/4733
Identification Number: DOI: 10.1002/andp.201500144
Publisher: Wiley
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