Towards many-dimensional real-time quantum theory for heavy-particle dynamics. II. Beyond semiclassics by quantum smoothing of the singularity in quantum-classical correspondence.

A theory of many-dimensional real-time quantum dynamics is studied in terms of action decomposed function (ADF), a class of quantum wave function. In the preceding companion paper [ S. Takahashi and K. Takatsuka Phys. Rev. A 89 012108 (2014)], we showed that semiclassical dynamics for ADF in the Lagrange picture of phase flow can be described in terms of what we call deviation determinant and associated quantum phases without use of the stability matrix. Consequently, the Hessian of the involved potential functions is not required in this formalism. This paper is devoted to an analysis of the mechanism of quantum diffusion (quantum smoothing) that removes the singularity inherent in the semiclassical ADF: We derive a Lorentzian form for the amplitude factor of ADF. The real part of its denominator comes from the deviation determinant, while the imaginary part reflects quantum diffusion and is proportional to the Planck constant. The presence of the nonzero imaginary part smooths out the singularity and removes the divergence. Besides, this imaginary part can be obtained through a Wronskian relation with the deviation vectors, which can be solved rather easily at each space-time point on a classical trajectory. A number of theoretical advantages of the Lorentzian form and the Wronskian relation are illustrated theoretically and numerically. It turns out that there is no essential difficulty in applications to many-dimensional heavy-particle systems such as molecules. The theory is examined with stringent numerical tests. [ABSTRACT FROM AUTHOR]