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Updated: Jul 4, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Variational Lang-Firsov Approach Plus Møller-Plesset Perturbation Theory with Applications to Ab Initio Polariton
Zhi-Hao Cui1, Arkajit Mandal1, David R Reichman1
1Department of Chemistry, Columbia University, 3000 Broadway, New York, New York 10027, United States.
Abstract:
We apply the Lang-Firsov (LF) transformation to electron-boson coupled Hamiltonians and variationally optimize the transformation parameters and molecular orbital coefficients to determine the ground state. Møller-Plesset (MP-n, with n = 2 and 4) perturbation theory is then applied on top of the optimized LF mean-field state to improve the description of electron-electron and electron-boson correlations. The method (LF-MP) is applied to several electron-boson coupled systems, including the Hubbard-Holstein model, diatomic molecule dissociation (H2, HF), and the modification of proton transfer reactions (malonaldehyde and aminopropenal) via the formation of polaritons in an optical cavity. We show that with a correction for the electron-electron correlation, the method gives quantitatively accurate energies comparable to that by exact diagonalization or coupled-cluster theory. The effects of multiple photon modes, spin polarization, and the comparison to the coherent state MP theory are also discussed.
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