Compact Bases for Vibronic Coupling in Spectral Simulations: The Photoelectron Spectrum of Cyclopentoxide in the Full 39 Internal Modes.

We report an algorithm to automatically generate compact multimode vibrational bases for the Köppel-Domcke-Cederbaum (KDC) vibronic coupling wave function used in spectral simulations of moderate-sized molecules. As a full quantum method, the size of the vibronic expansion grows exponentially with respect to the number of vibrational modes, necessitating compact bases for moderate-sized systems. The problem of generating such a basis consists of two parts: one is the choice of vibrational normal modes, and the other is the number of phonons allowed in each mode. A previously developed final-state-biased technique addresses the former part, and this work focuses on the latter part: proposing an algorithm for generating an optimal phonon distribution. By virtue of this phonon distribution, compact and affordable bases can be automatically generated for systems with on the order of 15 atoms. Our algorithm is applied to determine the nonadiabatic photoelectron spectrum of cyclopentoxide in the full 39 internal modes.