Algebraic approach to electronic spectroscopy and dynamics

Abstract

Lie algebra, Zassenhaus, and parameter differentiation techniques are utilized to break up the exponential of a bilinear Hamiltonian operator into a product of noncommuting exponential operators by the virtue of the theory of Wei and Norman [J. Math. Phys. 4, 575 (1963); Proc. Am. Math. Soc., 15, 327 (1964)]. There are about three different ways to find the Zassenhaus exponents, namely, binomial expansion, Suzuki formula, and q-exponential transformation. A fourth, and most reliable method, is provided. Since linearly displaced and distorted (curvature change upon excitation/emission) Hamiltonian and spin-boson Hamiltonian may be classified as bilinear Hamiltonians, the presented algebraic algorithm (exponential operator disentanglement exploiting six-dimensional Lie algebra case) should be useful in spin-boson problems. The linearly displaced and distorted Hamiltonian exponential is only treated here. While the spin-boson model is used here only as a demonstration of the idea, the herein approach is more general and powerful than the specific example treated. The optical linear dipole moment correlation function is algebraically derived using the above mentioned methods and coherent states. Coherent states are eigenvectors of the bosonic lowering operator a and not of the raising operator a(+). While exp(a(+)) translates coherent states, exp(a(+)a(+)) operation on coherent states has always been a challenge, as a(+) has no eigenvectors. Three approaches, and the results, of that operation are provided. Linear absorption spectra are derived, calculated, and discussed. The linear dipole moment correlation function for the pure quadratic coupling case is expressed in terms of Legendre polynomials to better show the even vibronic transitions in the absorption spectrum. Comparison of the present line shapes to those calculated by other methods is provided. Franck-Condon factors for both linear and quadratic couplings are exactly accounted for by the herein calculated linear absorption spectra. This new methodology should easily pave the way to calculating the four-point correlation function, F(tau(1),tau(2),tau(3),tau(4)), of which the optical nonlinear response function may be procured, as evaluating F(tau(1),tau(2),tau(3),tau(4)) is only evaluating the optical linear dipole moment correlation function iteratively over different time intervals, which should allow calculating various optical nonlinear temporal/spectral signals.