Transcorrelated Methods for Multireference Problems
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arXiv
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| Autori principali: | , , , , , |
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| Natura: | Preprint |
| Pubblicazione: |
2025
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| _version_ | 1866910969047810048 |
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| author | Haupt, J. Philip Christlmaier, Evelin M. C. Ríos, Pablo López Bogdanov, Nikolay A. Kats, Daniel Alavi, Ali |
| author_facet | Haupt, J. Philip Christlmaier, Evelin M. C. Ríos, Pablo López Bogdanov, Nikolay A. Kats, Daniel Alavi, Ali |
| contents | We apply the transcorrelated method to problems of multireference character. For this, we show that the choice of reference wavefunction during the Jastrow optimisation procedure is vital, and we propose a workflow wherein we use conventional multi-configurational methods to provide a reference wavefunction for Jastrow factor optimisation. This Jastrow function is subsequently used with transcorrelated-full configuration interaction quantum Monte Carlo within the xTC approximation (TC-FCIQMC) to yield highly accurate transcorrelated energies. This is demonstrated for N$_2$ using the aug-cc-pVTZ basis set, achieving chemical accuracy across the entire binding curve compared with experiment. We also apply the method to compute excitation energies of dinitrogen, CO and the ammonia molecule, where accurate results, comparable to the best available theoretical predictions, are obtained with modest basis sets. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2505_20187 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Transcorrelated Methods for Multireference Problems Haupt, J. Philip Christlmaier, Evelin M. C. Ríos, Pablo López Bogdanov, Nikolay A. Kats, Daniel Alavi, Ali Chemical Physics Computational Physics We apply the transcorrelated method to problems of multireference character. For this, we show that the choice of reference wavefunction during the Jastrow optimisation procedure is vital, and we propose a workflow wherein we use conventional multi-configurational methods to provide a reference wavefunction for Jastrow factor optimisation. This Jastrow function is subsequently used with transcorrelated-full configuration interaction quantum Monte Carlo within the xTC approximation (TC-FCIQMC) to yield highly accurate transcorrelated energies. This is demonstrated for N$_2$ using the aug-cc-pVTZ basis set, achieving chemical accuracy across the entire binding curve compared with experiment. We also apply the method to compute excitation energies of dinitrogen, CO and the ammonia molecule, where accurate results, comparable to the best available theoretical predictions, are obtained with modest basis sets. |
| title | Transcorrelated Methods for Multireference Problems |
| topic | Chemical Physics Computational Physics |
| url | https://arxiv.org/abs/2505.20187 |