Analytic route to tunneling splittings using semiclassical perturbation theory
We present an efficient, analytical, and simple route to approximating tunneling splittings in multidimensional chemical systems, directly from ab initio computations. The method is based on the Wentzel–Kramers–Brillouin (WKB) approximation combined with the vibrational perturbation theory. Anharmon...
| Main Authors: | , |
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| Format: | Journal article |
| Language: | English |
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American Chemical Society
2020
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| _version_ | 1826283738702544896 |
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| author | Burd, TAH Clary, DC |
| author_facet | Burd, TAH Clary, DC |
| author_sort | Burd, TAH |
| collection | OXFORD |
| description | We present an efficient, analytical, and simple route to approximating tunneling splittings in multidimensional chemical systems, directly from ab initio computations. The method is based on the Wentzel–Kramers–Brillouin (WKB) approximation combined with the vibrational perturbation theory. Anharmonicity and corner-cutting effects are implicitly accounted for without requiring a full potential energy surface. We test this method on the following three systems: a model one-dimensional double-well potential, the isomerization of malonaldehyde, and the isomerization of tropolone. The method is shown to be efficient and reliable.
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| first_indexed | 2024-03-07T01:03:25Z |
| format | Journal article |
| id | oxford-uuid:8a7dd2f1-22e1-4fc6-8ec9-26e3c5e6637e |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-03-07T01:03:25Z |
| publishDate | 2020 |
| publisher | American Chemical Society |
| record_format | dspace |
| spelling | oxford-uuid:8a7dd2f1-22e1-4fc6-8ec9-26e3c5e6637e2022-03-26T22:32:00ZAnalytic route to tunneling splittings using semiclassical perturbation theoryJournal articlehttp://purl.org/coar/resource_type/c_dcae04bcuuid:8a7dd2f1-22e1-4fc6-8ec9-26e3c5e6637eEnglishSymplectic ElementsAmerican Chemical Society2020Burd, TAHClary, DCWe present an efficient, analytical, and simple route to approximating tunneling splittings in multidimensional chemical systems, directly from ab initio computations. The method is based on the Wentzel–Kramers–Brillouin (WKB) approximation combined with the vibrational perturbation theory. Anharmonicity and corner-cutting effects are implicitly accounted for without requiring a full potential energy surface. We test this method on the following three systems: a model one-dimensional double-well potential, the isomerization of malonaldehyde, and the isomerization of tropolone. The method is shown to be efficient and reliable. |
| spellingShingle | Burd, TAH Clary, DC Analytic route to tunneling splittings using semiclassical perturbation theory |
| title | Analytic route to tunneling splittings using semiclassical perturbation theory |
| title_full | Analytic route to tunneling splittings using semiclassical perturbation theory |
| title_fullStr | Analytic route to tunneling splittings using semiclassical perturbation theory |
| title_full_unstemmed | Analytic route to tunneling splittings using semiclassical perturbation theory |
| title_short | Analytic route to tunneling splittings using semiclassical perturbation theory |
| title_sort | analytic route to tunneling splittings using semiclassical perturbation theory |
| work_keys_str_mv | AT burdtah analyticroutetotunnelingsplittingsusingsemiclassicalperturbationtheory AT clarydc analyticroutetotunnelingsplittingsusingsemiclassicalperturbationtheory |