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| Format: | Preprint |
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2024
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| Online Access: | https://arxiv.org/abs/2405.05041 |
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| _version_ | 1866917661410066432 |
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| author | Luu, Du Corminboeuf, Clemence Patkowski, Konrad |
| author_facet | Luu, Du Corminboeuf, Clemence Patkowski, Konrad |
| contents | Symmetry-adapted perturbation theory (SAPT) is a popular and versatile tool to compute and decompose noncovalent interaction energies between molecules. The intramolecular SAPT (ISAPT) variant provides a similar energy decomposition between two nonbonded fragments of the same molecule, covalently connected by a third fragment. In this work, we explore an alternative approach where the noncovalent interaction is singled out by a range separation of the Coulomb potential. We investigate two common splittings of the $1/r$ potential into long-range and short-range parts based on the Gaussian and error functions, and approximate either the entire intermolecular/interfragment interaction or only its attractive terms by the long-range contribution. These range separation schemes are tested for a number of intermolecular and intramolecular complexes. We find that the energy corrections from range-separated SAPT or ISAPT are in reasonable agreement with complete SAPT/ISAPT data. This result should be contrasted with the inability of the long-range multipole expansion to describe crucial short-range charge penetration and exchange effects; it shows that the long-range interaction potential does not just recover the asymptotic interaction energy but also provides a useful account of short-range terms. The best consistency is attained for the error-function separation applied to all interaction terms, both attractive and repulsive. This study is the first step towards a fragmentation-free decomposition of intramolecular nonbonded energy. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2405_05041 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Range separation of the interaction potential in intermolecular and intramolecular symmetry-adapted perturbation theory Luu, Du Corminboeuf, Clemence Patkowski, Konrad Chemical Physics Symmetry-adapted perturbation theory (SAPT) is a popular and versatile tool to compute and decompose noncovalent interaction energies between molecules. The intramolecular SAPT (ISAPT) variant provides a similar energy decomposition between two nonbonded fragments of the same molecule, covalently connected by a third fragment. In this work, we explore an alternative approach where the noncovalent interaction is singled out by a range separation of the Coulomb potential. We investigate two common splittings of the $1/r$ potential into long-range and short-range parts based on the Gaussian and error functions, and approximate either the entire intermolecular/interfragment interaction or only its attractive terms by the long-range contribution. These range separation schemes are tested for a number of intermolecular and intramolecular complexes. We find that the energy corrections from range-separated SAPT or ISAPT are in reasonable agreement with complete SAPT/ISAPT data. This result should be contrasted with the inability of the long-range multipole expansion to describe crucial short-range charge penetration and exchange effects; it shows that the long-range interaction potential does not just recover the asymptotic interaction energy but also provides a useful account of short-range terms. The best consistency is attained for the error-function separation applied to all interaction terms, both attractive and repulsive. This study is the first step towards a fragmentation-free decomposition of intramolecular nonbonded energy. |
| title | Range separation of the interaction potential in intermolecular and intramolecular symmetry-adapted perturbation theory |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2405.05041 |