2011/11/30 by Joonsuk Huh, Robert Berger
Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Cumulant #Dipole #Discrete dipole approximation #Distribution (mathematics) #Edgeworth series #Function (biology) #Harmonic #Harmonic oscillator #Spectroscopy and Quantum Chemical Studies #Synthesis and Properties of Aromatic Compounds #Vibronic spectroscopy #physics.chem-ph
paper · pdf · doi:10.1038/s41598-017-17506-8
published as Scientific Reports 7, Article number: 17561 (2017) · 7 pages, 1 figure; complexity discussed, method section significantly extended, computational details added, technical details explained, additional references included
openalex created_date 2016/08/23 · arxiv created 2017/08/27 · openalex publication_date 2017/12/08 · arxiv updated 2017/12/19 · openalex updated_date 2026/08/05
Abstract When existing, cumulants can provide valuable information about a given distribution and can in principle be used to either fully reconstruct or approximate the parent distribution function. A previously reported cumulant expansion approach for Franck–Condon profiles [Faraday Discuss., 150, 363 (2011)] is extended to describe also the profiles of vibronic transitions that are weakly allowed or forbidden in the Franck–Condon approximation (non-Condon profiles). In the harmonic approximation the cumulants of the vibronic profile can be evaluated analytically and numerically with a coherent state-based generating function that accounts for the Duschinsky effect. As illustration, the one-photon 1 1 A g → 1 1 B 2u UV absorption profile of benzene in the electric dipole and (linear) Herzberg–Teller approximation is presented herein for zero Kelvin and finite temperatures.