Application of time-independent cumulant expansion to calculation of Franck–Condon profiles for large molecular systems

Abstract

In this contribution, advantages and disadvantages of the time-independent and time-dependent approaches for Franck–Condon profile calculations are discussed within the displaced–distorted–rotated harmonic oscillator approximation. Particular strengths and prospects of a previously developed time-independent cumulant expansion in the calculation of a Franck–Condon profile for UV/Vis absorption spectra are demonstrated for the specific case of the S₀(¹A_g) → S₁(¹B_3u) transition of terrylene at various temperatures.