A general relationship is established between semiclassical and centroid-based methods for calculating real-time quantum-mechanical correlation functions. It is first shown that the linearized semiclassical initial-value-representation (LSC-IVR) approximation can be obtained via direct linearization of the forward-backward action in the exact path integral expression for the correlation function. A Kubo-transformed two-time correlation function, with the position operator as one of the two operators, is then cast in terms of a carefully crafted exact path integral expression. Linearization of the corresponding forward–backward action, supplemented by the assumption that the dynamics of the centroid is decoupled from that of the higher normal modes, is then shown to lead to the centroid correlation function.
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8 May 2003
Research Article|
May 08 2003
A relationship between semiclassical and centroid correlation functions
Qiang Shi;
Qiang Shi
Department of Chemistry and The FOCUS Center, University of Michigan, Ann Arbor, Michigan 48109-1055
Search for other works by this author on:
Eitan Geva
Eitan Geva
Department of Chemistry and The FOCUS Center, University of Michigan, Ann Arbor, Michigan 48109-1055
Search for other works by this author on:
Qiang Shi
Eitan Geva
Department of Chemistry and The FOCUS Center, University of Michigan, Ann Arbor, Michigan 48109-1055
J. Chem. Phys. 118, 8173–8184 (2003)
Article history
Received:
December 03 2002
Accepted:
February 10 2003
Citation
Qiang Shi, Eitan Geva; A relationship between semiclassical and centroid correlation functions. J. Chem. Phys. 8 May 2003; 118 (18): 8173–8184. https://doi.org/10.1063/1.1564814
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