Published in

Taylor and Francis Group, Molecular Physics, 21-22(102), p. 2285-2295, 2004

DOI: 10.1080/00268970412331290652

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Rovibronic spectroscopy of the van der Waals complex He–HCl+

Journal article published in 2004 by G. Dhont, G. Chambaud, G. C. Groenenboom ORCID, A. Van Der Avoird *
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

The potential energy surfaces and the calculated rovibronic spectrum of the electronic ground state of the van der Waals He–HCl+ cation are presented. The system is in a X 2Π electronic state at linearity, which splits into an A′ and an A″ state upon bending, leading to a Renner–Teller effect. Three-dimensional potential energy surfaces have been determined using the partially spin-restricted open-shell single and double excitation coupled cluster method with perturbative triples [RCCSD(T)]. The absolute minimum of a two-dimensional surface with the diatom bond length r fixed at r e = 2.489 a 0 is located at the linear He–HCl+ geometry with a van der Waals bond length R of 5.98 a 0 and D e 300 cm−1. The minimum in the full three-dimensional potential occurs for a slightly larger value of r: 2.492 a 0. The rovibronic levels of the He–HCl+ complex have been computed by a variational method for total angular momenta J =1/2, 3/2, 5/2, 7/2 and 9/2. The binding energy D 0 is calculated as 161.5 cm−1 using the two-dimensional potential energy surfaces with r frozen at r e and as 163.5 cm−1 in full three-dimensional calculations. Owing to the large and negative value of the spin–orbit parameter in HCl+ (A SO = −648.13 cm−1), all the considered rovibronic states correspond to the |Ω| = 3/2 spin–orbit component of HCl+. The nuclear wave functions of the complex could be interpreted using the model of a slightly hindered diatomic rotor. The energy level pattern and wave functions have been compared with the more floppy Ar–OH complex on the one hand and the more rigid He–HF+ system on the other. The anisotropy of the potential energy surface of the He–HCl+ complex is intermediate between these two cases and the rovibronic states reflect this property.