Accurate potential energy curves for HeH + isotopologues

Wei Cheng Tung, Michele Pavanello, Ludwik Adamowicz

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15 Scopus citations

Abstract

New accurate ground-state potential energy curves (PEC) for the 4HeH +, 4HeD +, 3HeH +, and 3HeD + isotopologues are calculated with 600 explicitly correlated Gaussian (ECG) functions with shifted centers in the range between R = 0.35 a 0 and 145 a 0. The calculations include the adiabatic corrections (AC). The absolute accuracy of all Born-Oppenheimer (BO) PEC points is better than 0.0018 cm -1 and it is better than 0.0005 cm -1 for the ACs. With respect to the very recent BO PEC calculations performed by Pachucki with 20 000 generalized Heitler-London explicitly correlated functions [K. Pachucki, Phys. Rev. A 85, 042511 (2012)]10.1103/PhysRevA.85.042511, the present energy calculated at R = 1.46 a 0 (a point near the BO equilibrium distance) lies above by only 0.0012 cm -1. Using Pachuckis BO energy at the equilibrium distance of R = 1.463 283 a 0, and the adiabatic corrections calculated in this work for the 4HeH +, 4HeD +, 3HeH +, and 3HeD + isotopologues, the following values are obtained for their PEC depths: 16 448.99893 cm -1, 16 456.86246 cm -1, 16 451.50635 cm -1, and 16 459.36988 cm -1, respectively. We also calculate the rovibrational (rovib) frequencies for the four isotopologues using the BO PEC of Pachucki augmented with the present ACs. The improvements over the BO+AC PEC of Bishop and Cheung (BC) [J. Mol. Spectrosc. 75, 462 (1979)]10.1016/0022-2852(79)90090-0 are 1.522 cm -1 at R = 4.5 a 0 and 0.322 cm -1 at R . To partially account for the nonadiabatic effects in the rovib calculations an effective reduced-mass approach is used. With that, the present 4HeH + rovibrational transitions are considerably improved over the BC transitions as compared with the experimental values. Now the rovibrational transitions near the dissociation limit are as well reproduced by the present calculations as the lower transitions. For example, for the 4HeD + transitions corresponding to the ν = 13-9 hot bands the results are off from the experimental values by less than 0.023 cm -1. This confirms high accuracy of the present PECs at larger internuclear separations.

Original languageEnglish (US)
Article number164305
JournalJournal of Chemical Physics
Volume137
Issue number16
DOIs
StatePublished - Oct 28 2012

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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