Mean-Field Ring Polymer Rates Using a Population Dividing Surface
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arXiv
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| Main Authors: | , , , |
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| Format: | Preprint |
| Published: |
2024
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| _version_ | 1866910438207258624 |
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| author | London, Nathan Bu, Siyu Johnson, Britta Ann Ananth, Nandini |
| author_facet | London, Nathan Bu, Siyu Johnson, Britta Ann Ananth, Nandini |
| contents | Mean-field Ring Polymer Molecular Dynamics (MF-RPMD) offers a computationally efficient method for the simulation of reaction rates in multi-level systems. Previous work has established that, to model a nonadiabatic state-to-state reaction accurately, the dividing surface must be chosen to explicitly sample kinked ring polymer configurations where at least one bead is in a different electronic state than the others. Building on this, we introduce a population difference coordinate and a kink-constrained dividing surface, and we test the accuracy of the resulting mean-field rate theory on a series of linear vibronic coupling model systems as well as spin-boson models. We demonstrate that this new MF-RPMD rate approach is efficient to implement and quantitatively accurate for models over a wide range of driving forces, coupling strengths, and temperatures. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2405_04613 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Mean-Field Ring Polymer Rates Using a Population Dividing Surface London, Nathan Bu, Siyu Johnson, Britta Ann Ananth, Nandini Chemical Physics Mean-field Ring Polymer Molecular Dynamics (MF-RPMD) offers a computationally efficient method for the simulation of reaction rates in multi-level systems. Previous work has established that, to model a nonadiabatic state-to-state reaction accurately, the dividing surface must be chosen to explicitly sample kinked ring polymer configurations where at least one bead is in a different electronic state than the others. Building on this, we introduce a population difference coordinate and a kink-constrained dividing surface, and we test the accuracy of the resulting mean-field rate theory on a series of linear vibronic coupling model systems as well as spin-boson models. We demonstrate that this new MF-RPMD rate approach is efficient to implement and quantitatively accurate for models over a wide range of driving forces, coupling strengths, and temperatures. |
| title | Mean-Field Ring Polymer Rates Using a Population Dividing Surface |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2405.04613 |