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arXiv · 2310.13084

Variational Lang-Firsov approach plus M\o{}ller-Plesset perturbation theory with applications to ab initio polariton chemistry

Zhi-Hao Cui·Arkajit Mandal·David R. Reichman
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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. M\o{}ller-Plesset (MP-$n$, with $n = 2$ and $4$) perturbation theory is then performed 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 ($\text{H}_2$, $\text{HF}$), 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 exact diagonalization or coupled-cluster theory. The effect of multiple photon modes, spin polarization, and the comparison to the coherent state MP theory are also discussed.

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Zhi-Hao Cui, Arkajit Mandal, David R. Reichman. 2023-10-19. Variational Lang-Firsov approach plus M\o{}ller-Plesset perturbation theory with applications to ab initio polariton chemistry. https://doi.org/10.1021/acs.jctc.3c01166

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