In this paper we show how it is possible to treat the quantum vibrational relaxation of a chromophore, embedded in a complex atomic-molecular environment, via the explicit solution of the time-dependent Schroedinger equation once using a proper separation between quantum and semiclassical degrees of freedom. The rigorous theoretical framework derived, based on first principles and making use of well defined approximations/assumptions, is utilized to construct a general model for the kinetics of the vibrational relaxation as obtained by the direct evaluation of the density matrix for all the relevant quantum state transitions. Application to (deuterated) N-methylacetamide (the typical benchmark used as a model for the amino acids) shows that the obtained theoretical-computational approach captures the essential features of the experimental process, unveiling the basic relaxation mechanism involving several vibrational state transitions.

Amadei, A., Aschi, M. (2019). Modelling vibrational relaxation in complex molecular systems. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 21(36), 20003-20017 [10.1039/c9cp03379c].

Modelling vibrational relaxation in complex molecular systems

Amadei A.;Aschi M.
2019-01-01

Abstract

In this paper we show how it is possible to treat the quantum vibrational relaxation of a chromophore, embedded in a complex atomic-molecular environment, via the explicit solution of the time-dependent Schroedinger equation once using a proper separation between quantum and semiclassical degrees of freedom. The rigorous theoretical framework derived, based on first principles and making use of well defined approximations/assumptions, is utilized to construct a general model for the kinetics of the vibrational relaxation as obtained by the direct evaluation of the density matrix for all the relevant quantum state transitions. Application to (deuterated) N-methylacetamide (the typical benchmark used as a model for the amino acids) shows that the obtained theoretical-computational approach captures the essential features of the experimental process, unveiling the basic relaxation mechanism involving several vibrational state transitions.
Pubblicato
Rilevanza internazionale
Articolo
Esperti anonimi
Settore CHIM/02
English
Amadei, A., Aschi, M. (2019). Modelling vibrational relaxation in complex molecular systems. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 21(36), 20003-20017 [10.1039/c9cp03379c].
Amadei, A; Aschi, M
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/2108/243436
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