Matrix fluctuation-dissipation theorem: Application to quantum relaxation phenomena

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Abstract

We recently derived a matrix fluctuation-dissipation (MFD) theorem, which directly relates the spectral intensities to the eigenvalue fluctuations of a quantum system. Here additional properties of the MFD theorem are presented. MFD is a microcanonical version of the fluctuation-dissipation theorem for a single high-energy state embedded in a dissipative quantum-mechanical bath. This is useful in applications to vibrational relaxation, which can be exactly described by the MFD formula if a single initial state carries all the oscillator strength. MFD versions of formulas for the dilution factor (σ) and fraction of occupied phase space (F) are derived, which can be used to compute these quantities exactly without knowledge of the eigenfunctions. Computational applications are given in a companion paper.

Original languageEnglish (US)
Pages (from-to)12178-12182
Number of pages5
JournalJournal of physical chemistry
Volume100
Issue number30
DOIs
StatePublished - Jul 25 1996

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

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