Interpolation of intermolecular potentials using Gaussian processes
A procedure is proposed to produce intermolecular potential energy surfaces from limited data. The procedure involves generation of geometrical configurations using a Latin hypercube design, with a maximin criterion, based on inverse internuclear distances. Gaussian processes are used to interpolate...
| Main Authors: | , , , |
|---|---|
| Format: | Article |
| Published: |
American Institute of Physics Publishing
2017
|
| Online Access: | https://eprints.nottingham.ac.uk/43469/ |
| _version_ | 1848796695567007744 |
|---|---|
| author | Uteva, Elena Graham, Richard Stuart Wilkinson, Richard D. Wheatley, Richard J. |
| author_facet | Uteva, Elena Graham, Richard Stuart Wilkinson, Richard D. Wheatley, Richard J. |
| author_sort | Uteva, Elena |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | A procedure is proposed to produce intermolecular potential energy surfaces from limited data. The procedure involves generation of geometrical configurations using a Latin hypercube design, with a maximin criterion, based on inverse internuclear distances. Gaussian processes are used to interpolate the data, using over-specified inverse molecular distances as covariates, greatly improving the interpolation. Symmetric covariance functions are specified so that the interpolation surface obeys all relevant symmetries, reducing prediction errors. The interpolation scheme can be applied to many important molecular interactions with trivial modifications. Results are presented for three systems involving CO2, a system with a deep energy minimum (HF - HF) and a system with 48 symmetries (CH4 - N2). In each case the procedure accurately predicts an independent test set. Training this method with high-precision ab initio evaluations of the CO2 - CO interaction enables a parameter-free, first-principles prediction of the CO2 - CO cross virial coefficient that agree very well with experiments. |
| first_indexed | 2025-11-14T19:52:04Z |
| format | Article |
| id | nottingham-43469 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:52:04Z |
| publishDate | 2017 |
| publisher | American Institute of Physics Publishing |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-434692020-05-04T18:52:01Z https://eprints.nottingham.ac.uk/43469/ Interpolation of intermolecular potentials using Gaussian processes Uteva, Elena Graham, Richard Stuart Wilkinson, Richard D. Wheatley, Richard J. A procedure is proposed to produce intermolecular potential energy surfaces from limited data. The procedure involves generation of geometrical configurations using a Latin hypercube design, with a maximin criterion, based on inverse internuclear distances. Gaussian processes are used to interpolate the data, using over-specified inverse molecular distances as covariates, greatly improving the interpolation. Symmetric covariance functions are specified so that the interpolation surface obeys all relevant symmetries, reducing prediction errors. The interpolation scheme can be applied to many important molecular interactions with trivial modifications. Results are presented for three systems involving CO2, a system with a deep energy minimum (HF - HF) and a system with 48 symmetries (CH4 - N2). In each case the procedure accurately predicts an independent test set. Training this method with high-precision ab initio evaluations of the CO2 - CO interaction enables a parameter-free, first-principles prediction of the CO2 - CO cross virial coefficient that agree very well with experiments. American Institute of Physics Publishing 2017-06-26 Article PeerReviewed Uteva, Elena, Graham, Richard Stuart, Wilkinson, Richard D. and Wheatley, Richard J. (2017) Interpolation of intermolecular potentials using Gaussian processes. Journal of Chemical Physics, 147 . 161706/1-161706/7. ISSN 1089-7690 http://aip.scitation.org/doi/10.1063/1.4986489 doi:10.1063/1.4986489 doi:10.1063/1.4986489 |
| spellingShingle | Uteva, Elena Graham, Richard Stuart Wilkinson, Richard D. Wheatley, Richard J. Interpolation of intermolecular potentials using Gaussian processes |
| title | Interpolation of intermolecular potentials using Gaussian processes |
| title_full | Interpolation of intermolecular potentials using Gaussian processes |
| title_fullStr | Interpolation of intermolecular potentials using Gaussian processes |
| title_full_unstemmed | Interpolation of intermolecular potentials using Gaussian processes |
| title_short | Interpolation of intermolecular potentials using Gaussian processes |
| title_sort | interpolation of intermolecular potentials using gaussian processes |
| url | https://eprints.nottingham.ac.uk/43469/ https://eprints.nottingham.ac.uk/43469/ https://eprints.nottingham.ac.uk/43469/ |