Tennyson, J.;
Barletta, P.;
Kostin, M.A.;
Polyansky, O.L.;
Zobov, N.F.;
(2002)
Ab initio rotation–vibration energy levels of triatomics to
spectroscopic accuracy.
Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
, 58
(4)
pp. 663-672.
10.1016/S1386-1425(01)00663-1.
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Abstract
The factors that need to be taken into account to achieve spectroscopic accuracy for triatomic molecules are considered focusing on H3+ and water as examples. The magnitude of the adiabatic and non-adiabatic corrections to the Born–Oppenheimer approximation is illustrated for both molecules, and methods of including them ab initio are discussed. Electronic relativistic effects are not important for H3+, but are for water for which the magnitude of the various effects is discussed. For H3+ inclusion of rotational non-adiabatic effects means that levels can be generated to an accuracy approaching 0.01 cm−1; for water the error is still dominated by the error in the correlation energy in the electronic structure calculation. Prospects for improving this aspect of the calculation are discussed.
| Type: | Article |
|---|---|
| Title: | Ab initio rotation–vibration energy levels of triatomics to spectroscopic accuracy |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/S1386-1425(01)00663-1 |
| Publisher version: | http://dx.doi.org/10.1016/S1386-1425(01)00663-1 |
| Language: | English |
| Keywords: | rotation–vibration energy, relativistic effects, triatomic molecules |
| UCL classification: | UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Physics and Astronomy |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/1162 |
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