Distinction of photoelectron spectroscopy of cis- and trans-acrolein explored by theoretical computation

Chang, Jia‐Lin; Jen, Chi-Chang; Huang, Yun-Jhu; Du, Zong-Kun

doi:10.1016/j.chemphys.2021.111166

Cited by 2 publications

(1 citation statement)

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“…In the past decade, we have developed some approaches for computing FCFs of harmonic oscillators. ,− The Duschinsky effect has been taken into account in our model for polyatomic molecules . Our harmonic model for computing FCFs has been successfully applied to the studies of the PES of some molecules. − However, the excitation energies computed by the harmonic model are usually larger than the experimental values. Accordingly, we constructed a hybrid model of harmonic and anharmonic oscillators to compute the FCFs and simulate the vibronic spectra of the molecules in this study.…”

Section: Introductionmentioning

confidence: 99%

Reassignment of the Photoelectron Spectrum of Methylketene Using a Hybrid Model of Harmonic and Anharmonic Oscillators to Compute Franck–Condon Factors

Chang,

Chen,

Huang

2023

ACS Omega

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We constructed a hybrid model of harmonic and anharmonic oscillators to compute Franck–Condon factors and interpret the photoelectron spectrum of methylketene. The equilibrium structures of methylketene and its cation were optimized, and then, the harmonic and anharmonic vibrational frequencies were computed using the B3LYP, PBE0, APFD, and ωB97XD approaches of the density functional theory. The photoelectron spectrum of methylketene was simulated by computing the Franck–Condon factors with both the harmonic and hybrid models. The adiabatic ionization energy of methylketene was computed by using the CCSD(T) approach extrapolating to the complete basis set limit. The simulated photoelectron spectra are consistent with those from the experiment for both the harmonic and hybrid models. However, the error in band positions is reduced by using the hybrid model. The computed adiabatic ionization energies of methylketene are in agreement with the experiment, with the smallest error being 0.017 eV. Our interpretation based on the theoretical spectrum led to the reassignment of the experimental photoelectron spectrum of methylketene.

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