Variational Lang-Firsov approach plus Møller-Plesset perturbation theory with applications to ab initio polariton chemistry
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| Format: | Preprint |
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2023
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| author | Cui, Zhi-Hao Mandal, Arkajit Reichman, David R. |
| author_facet | Cui, Zhi-Hao Mandal, Arkajit Reichman, David R. |
| contents | 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 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. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2310_13084 |
| institution | arXiv |
| publishDate | 2023 |
| record_format | arxiv |
| spellingShingle | Variational Lang-Firsov approach plus Møller-Plesset perturbation theory with applications to ab initio polariton chemistry Cui, Zhi-Hao Mandal, Arkajit Reichman, David R. Chemical Physics Materials Science Computational Physics 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 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. |
| title | Variational Lang-Firsov approach plus Møller-Plesset perturbation theory with applications to ab initio polariton chemistry |
| topic | Chemical Physics Materials Science Computational Physics |
| url | https://arxiv.org/abs/2310.13084 |