Double Configuration Interaction Singles: Scalable and size-intensive approach for orbital relaxation in excited states and bond-dissociation
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arXiv
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| Format: | Preprint |
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2024
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| _version_ | 1866914370601091072 |
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| author | Tsuchimochi, Takashi |
| author_facet | Tsuchimochi, Takashi |
| contents | We present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed method, which can be interpreted as a "CIS-then-CIS" scheme, variationally accounts for orbital relaxation in excited states, thus significantly reducing the overestimation of charge-transfer excitation energies commonly associated with standard CIS. Additionally, by incorporating de-excitation effects from CIS, we demonstrate that our approach effectively describes single bond dissociation. Notably, all these improvements are achieved at a mean-field cost, with the pre-factor further reduced with the efficient algorithm introduced here, while preserving the size-intensive property of CIS. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2410_09912 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Double Configuration Interaction Singles: Scalable and size-intensive approach for orbital relaxation in excited states and bond-dissociation Tsuchimochi, Takashi Chemical Physics We present a novel theoretical scheme for orbital relaxation in configuration interaction singles (CIS) based on a perturbative treatment of its electronic Hessian, whose analytical derivation is also established in this work. The proposed method, which can be interpreted as a "CIS-then-CIS" scheme, variationally accounts for orbital relaxation in excited states, thus significantly reducing the overestimation of charge-transfer excitation energies commonly associated with standard CIS. Additionally, by incorporating de-excitation effects from CIS, we demonstrate that our approach effectively describes single bond dissociation. Notably, all these improvements are achieved at a mean-field cost, with the pre-factor further reduced with the efficient algorithm introduced here, while preserving the size-intensive property of CIS. |
| title | Double Configuration Interaction Singles: Scalable and size-intensive approach for orbital relaxation in excited states and bond-dissociation |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2410.09912 |