In this paper, we examine how and when quantum evolution can be approximated in terms of (generalized) classical dynamics in calculations of correlation functions, with a focus on the symmetrized time correlation function introduced by Schofield. To that end, this function is expressed as a path integral in complex time and written in terms of sum and difference path variables. Taylor series expansion of the path integral's exponent to first and second order in the difference variables leads to two original developments. The first order expansion is used to obtain a simple, path integral based, derivation of the so-called Schofield's quantum correction factor. The second order result is employed to show how quantum mechanical delocalization manifests itself in the approximation of the correlation function and hinders, even in the semiclassical limit, the interpretation of the propagators in terms of sets of guiding classical trajectories dressed with appropriate weights.

Path integral based calculations of symmetrized time correlation functions. I / Bonella, Sara; Monteferrante, Michele; Carlo, Pierleoni; Ciccotti, Giovanni. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 133:16(2010), p. 164104. [10.1063/1.3493448]

Path integral based calculations of symmetrized time correlation functions. I.

BONELLA, SARA;MONTEFERRANTE, MICHELE;CICCOTTI, Giovanni
2010

Abstract

In this paper, we examine how and when quantum evolution can be approximated in terms of (generalized) classical dynamics in calculations of correlation functions, with a focus on the symmetrized time correlation function introduced by Schofield. To that end, this function is expressed as a path integral in complex time and written in terms of sum and difference path variables. Taylor series expansion of the path integral's exponent to first and second order in the difference variables leads to two original developments. The first order expansion is used to obtain a simple, path integral based, derivation of the so-called Schofield's quantum correction factor. The second order result is employed to show how quantum mechanical delocalization manifests itself in the approximation of the correlation function and hinders, even in the semiclassical limit, the interpretation of the propagators in terms of sets of guiding classical trajectories dressed with appropriate weights.
2010
01 Pubblicazione su rivista::01a Articolo in rivista
Path integral based calculations of symmetrized time correlation functions. I / Bonella, Sara; Monteferrante, Michele; Carlo, Pierleoni; Ciccotti, Giovanni. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 133:16(2010), p. 164104. [10.1063/1.3493448]
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11573/377353
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