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 a0 and 145 a0. 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)] https://doi.org/10.1103/PhysRevA.85.042511, the present energy calculated at R = 1.46 a0 (a point near the BO equilibrium distance) lies above by only 0.0012 cm−1. Using Pachucki's BO energy at the equilibrium distance of R = 1.463 283 a0, 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)] https://doi.org/10.1016/0022-2852(79)90090-0 are 1.522 cm−1 at R = 4.5 a0 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.
Skip Nav Destination
Article navigation
28 October 2012
Research Article|
October 23 2012
Accurate potential energy curves for HeH+ isotopologues
Wei-Cheng Tung;
Wei-Cheng Tung
1Department of Chemistry and Biochemistry,
University of Arizona
, Tucson, Arizona 85721, USA
Search for other works by this author on:
Michele Pavanello;
Michele Pavanello
2Department of Chemistry, Rutgers,
The State University of New Jersey
, Newark, New Jersey 07102, USA
Search for other works by this author on:
Ludwik Adamowicz
Ludwik Adamowicz
a)
1Department of Chemistry and Biochemistry,
University of Arizona
, Tucson, Arizona 85721, USA
Search for other works by this author on:
a)
Electronic mail: ludwik@u.arizona.edu
J. Chem. Phys. 137, 164305 (2012)
Article history
Received:
June 11 2012
Accepted:
October 01 2012
Citation
Wei-Cheng Tung, Michele Pavanello, Ludwik Adamowicz; Accurate potential energy curves for HeH+ isotopologues. J. Chem. Phys. 28 October 2012; 137 (16): 164305. https://doi.org/10.1063/1.4759077
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Pay-Per-View Access
$40.00
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.