Ovsyannikov, Roman I;
Makhnev, Vladimir;
Zobov, Nikolai F;
Koput, Jacek;
Tennyson, Jonathan;
Polyansky, Oleg L;
(2022)
Highly accurate HF dimer {\it ab initio} potential energy surface.
The Journal of Chemical Physics
10.1063/5.0083563.
(In press).
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Abstract
A very accurate, (HF)$_2$ potential energy surface (PES)is constructed based on \ai\ calculations performed% at the CCSD(T) level of theory with an aug-cc-pVQZ-F12basis set at about 152~000 points.A higher correlation correction is computed at CCSDT(Q) level for 2000 points and is considered alongside other more minorcorrections due to relativity, core-valence correlation and Born-Oppenheimer failure.The analytical surface constructed uses 500 constants to reproduce the \ai\ points with a standard deviation of 0.3 \cm.Vibration-rotation-inversion energy levels of the HF dimer are computed for this PES by variational solution of the nuclear-motionSchr\"{o}dinger using program WAVR4. Calculations over an extended range of rotationally excited states show very good agreementwith the experimental data. In particular the known empirical rotational constants $B$ for the ground vibrational states are predicted to better than about 2 MHz.$B$ constants for excited vibrational states are reproduced several times more accurately than by previous calculations. %The experimental dissociation energy of the HF dimer is reproduced \ai\ within the experimental accuracy of about 1 \cm\ for the first time. This level of accuracy is shown to extend to higher excited inter-molecular vibrational states $v$ and higher excited rotational quantum numbers $(J,K_a)$.
| Type: | Article |
|---|---|
| Title: | Highly accurate HF dimer {\it ab initio} potential energy surface |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1063/5.0083563 |
| Publisher version: | https://doi.org/10.1063/5.0083563 |
| Language: | English |
| Additional information: | ©2022 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (<ext-link ext-link-type="uri" href="http://creativecommons.org/licenses/by/4.0/">http://creativecommons.org/licenses/by/4.0/</ext-link>). |
| UCL classification: | UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy UCL > Provost and Vice Provost Offices > UCL BEAMS UCL |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10147555 |
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