Recent research developments in physical chemistry, Vol.9.

from which Franck-Condon factors were calculated and photoelectron spectra were simulated. The adiabatic ionization energies of vinyl alcohol were also computed by extrapolating the CCSD(T) energies to the complete basis set limit with aug-ccpVXZ (X ¼ D, T, Q, 5). The simulated photoelectron spectra of both vinyl alcohol and ovalene are in agreement with the experiments. The computed adiabatic ionization energies of synand anti-vinyl alcohol are in consistent with the experiment within 0.008 eV and 0.014 eV, respectively. We show, for the first time, that the analytical approach of computing FCIs is also efficient and promising for the studies of vibronic spectra of macrosystems. V C 2012 Wiley Periodicals, Inc.

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

The implementation, optimization, and performance of a generalized analytic treatment of multidimensional Franck–Condon Factors (FCF) within the harmonic oscillator approximation and associated photoelectron spectra (PES) for N-dimensional systems, including consideration of Eckart conditions in the displacement minimization and Cartesian coordinate handedness for evaluation of the Duschinsky Effect, is carried out in this work. A new efficient strategy for algorithmic efficiency for high dimensional systems is introduced, and demonstrated for 3-, 15-, and 30-dimensional systems. Determination of the photoelectron spectra for H2O+ (B2B2), vinyl alcohol, and C6H6+ (X2E1g) validates the capabilities with a high degree of accuracy with respect to experiment.

https://pubs.acs.org/doi/pdf/10.1021/acs.jctc.0c00594

An Efficient Analytic Approach for Calculation of Multi-Dimensional Franck–Condon Factors and Associated Photoelectron Spectra

A general analytical expression for the three-dimensional Franck–Condon integral and simulation of the photodetachment spectrum of the PO2-anion

An enhanced generalized analytic approach for determination of multidimensional Franck–Condon Factors (FCFs) enables efficient computational prediction of photoelectron spectra for large-dimensiona

Generalized Analytic Approach for Determination of Multidimensional Franck-Condon Factors: Simulated Photoelectron Spectra of Polynuclear Aromatic Hydrocarbons.

On the basis of the harmonic oscillator approximation, the two-dimensional four-mode Franck–Condon vibrational overlap integral under mode-mixing effects has been reduced to a product expression of one-dimensional Gaussian integrals with the aid of expanding Hermite polynomials. A more general analytical expression for the calculation of the two-dimensional four-mode Franck–Condon overlap integrals was derived by directly calculating the Gaussian integrals. This analytical expression was applied to investigate the photoelectron spectra of considering mode-mixing and hot band effects. Geometry optimizations and harmonic vibrational frequency calculations were performed on the  2A1 state of NO2 and the  1A1 state of . Franck–Condon analyses and spectral simulations were carried out on the NO2(  2A1)– (  1A1) photodetachment processes. The spectral simulations of vibrational structures based on the computed Franck–Condon factors are in excellent agreement with the observed spectra. In addition, the equilibri...

Xiuyuan Liang

Papers

A general analytical expression for the two-dimensional Franck–Condon integral and simulation of the photoelectron spectra of nitrogen dioxide

A combined ab initio and Franck–Condon simulation study of the photodetachment spectrum of the ClO2- anion