Ab initio instanton rate theory made efficient using Gaussian process regression
| LEADER | naa a22 4500 | ||
|---|---|---|---|
| 001 | 528786636 | ||
| 005 | 20180924065501.0 | ||
| 007 | cr unu---uuuuu | ||
| 008 | 180924s2018 xx s 000 0 eng | ||
| 024 | 7 | 0 | |a 10.3929/ethz-b-000290532 |2 doi |
| 024 | 7 | 0 | |a 10.1039/c8fd00085a |2 doi |
| 035 | |a (ETHRESEARCH)oai:www.research-collecti.ethz.ch:20.500.11850/290532 | ||
| 245 | 0 | 0 | |a Ab initio instanton rate theory made efficient using Gaussian process regression |h [Elektronische Daten] |c [Gabriel Laude, Danilo Calderini, David P. Tew, Jeremy O. Richardson] |
| 246 | 0 | |a Faraday discuss. | |
| 506 | |a Open access |2 ethresearch | ||
| 520 | 3 | |a Ab initio instanton rate theory is a computational method for rigorously including tunnelling effects into the calculations of chemical reaction rates based on a potential-energy surface computed on the fly from electronic-structure theory. This approach is necessary to extend conventional transition-state theory into the deep-tunnelling regime, but it is also more computationally expensive as it requires many more ab initio calculations. We propose an approach which uses Gaussian process regression to fit the potential-energy surface locally around the dominant tunnelling pathway. The method can be converged to give the same result as from an on-the-fly ab initio instanton calculation but it requires far fewer electronic-structure calculations. This makes it a practical approach for obtaining accurate rate constants based on high-level electronic-structure methods. We show fast convergence to reproduce benchmark H + CH4 results and evaluate new low-temperature rates of H + C2H6 in full dimensionality at a UCCSD(T)-F12b/cc-pVTZ-F12 level. | |
| 540 | |a Creative Commons Attribution 3.0 Unported |u http://creativecommons.org/licenses/by/3.0 |2 ethresearch | ||
| 700 | 1 | |a Laude |D Gabriel |e joint author | |
| 700 | 1 | |a Calderini |D Danilo |e joint author | |
| 700 | 1 | |a Tew |D David P. |e joint author | |
| 700 | 1 | |a Richardson |D Jeremy O. |e joint author | |
| 773 | 0 | |t Faraday Discussions |d London : Royal Society of Chemistry (RSC) |x 1359-6640 | |
| 856 | 4 | 0 | |u http://hdl.handle.net/20.500.11850/290532 |q text/html |z WWW-Backlink auf das Repository (Open access) |
| 908 | |D 1 |a Journal Article |2 ethresearch | ||
| 950 | |B ETHRESEARCH |P 856 |E 40 |u http://hdl.handle.net/20.500.11850/290532 |q text/html |z WWW-Backlink auf das Repository (Open access) | ||
| 950 | |B ETHRESEARCH |P 700 |E 1- |a Laude |D Gabriel |e joint author | ||
| 950 | |B ETHRESEARCH |P 700 |E 1- |a Calderini |D Danilo |e joint author | ||
| 950 | |B ETHRESEARCH |P 700 |E 1- |a Tew |D David P. |e joint author | ||
| 950 | |B ETHRESEARCH |P 700 |E 1- |a Richardson |D Jeremy O. |e joint author | ||
| 950 | |B ETHRESEARCH |P 773 |E 0- |t Faraday Discussions |d London : Royal Society of Chemistry (RSC) |x 1359-6640 | ||
| 898 | |a BK010053 |b XK010053 |c XK010000 | ||
| 949 | |B ETHRESEARCH |F ETHRESEARCH |b ETHRESEARCH |j Journal Article |c Open access | ||