The symmetrized quantum thermal flux operator

Abstract

Analysis of the symmetrized thermal flux operator leads to explicit expressions for its eigenvalues and eigenfunctions. At any point in configuration space one finds two nonzero eigenvalues of opposite sign. The associated eigenfunctions are L2 integrable. The eigenfunctions and eigenvalues are expressed in terms of the thermal density matrix in the vicinity of the transition state. The positive eigenvalue of the thermal flux operator gives an upper bound to the rate and allows for a formulation of a quantum mechanical variational transition state theory. This new upper bound, though, is only a slight improvement over previous theories.