Universität zu Köln

Harding, Michael E., Lipparini, Filippo ORCID: 0000-0002-4947-3912, Gauss, Juergen, Gerlich, Dieter, Schlemmer, Stephan ORCID: 0000-0002-1421-7281 and van der Avoird, Ad ORCID: 0000-0003-1856-240X (2022). The He-H-3(+) complex. I. Vibration-rotation-tunneling states and transition probabilities. J. Chem. Phys., 156 (14). MELVILLE: AIP Publishing. ISSN 1089-7690

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Abstract

With a He-H-3(+) interaction potential obtained from advanced electronic structure calculations, we computed the vibration-rotation-tunneling (VRT) states of this complex for total angular momenta J from 0 to 9, both for the vibrational ground state and for the twofold degenerate v(2) = 1 excited state of H. The potential has three equivalent global minima with depth D-e = 455.3 cm(-1) for He in the plane of H-3(+) , three equatorial saddle points that separate these minima with barriers of 159.5 cm(-1), and two axial saddle points with energies of 243.1 cm(-1) above the minima. The dissociation energies calculated for the complexes of He with ortho-H-3(+) (oH(3)(+)) and para-H-3(+) (pH(3)(+)) are D-0 = 234.5 and 236.3 cm(-1), respectively. Wave function plots of the VRT states show that they may be characterized as weakly hindered internal rotor states, delocalized over the three minima in the potential and with considerable amplitude at the barriers. Most of them are dominated by the j(k) = 1(0) and 1(1) rotational ground states of oH(3)(+) and pH(3)(+), with the intermolecular stretching mode excited up to v = 4 inclusive. However, we also found excited internal rotor states: 3(3) in He-oH(3)(+) , and 2(2) and 2(1) in He-pH(3). The VRT levels and wave functions were used to calculate the frequencies and line strengths of all allowed v(2) = 0 -> 1 rovibrational transitions in the complex. Theoretical spectra generated with these results are compared with the experimental spectra in Paper II [Salomon et al., J. Chem. Phys. 156, 144308 (2022)] and are extremely helpful in assigning these spectra. This comparison shows that the theoretical energy levels and spectra agree very well with the measured ones, which confirms the high accuracy of our ab initio He-H-3(+) interaction potential and of the ensuing calculations of the VRT states. Published under an exclusive license by AIP Publishing.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Harding, Michael E. UNSPECIFIED UNSPECIFIED UNSPECIFIED Lipparini, Filippo UNSPECIFIED orcid.org/0000-0002-4947-3912 UNSPECIFIED Gauss, Juergen UNSPECIFIED UNSPECIFIED UNSPECIFIED Gerlich, Dieter UNSPECIFIED UNSPECIFIED UNSPECIFIED Schlemmer, Stephan UNSPECIFIED orcid.org/0000-0002-1421-7281 UNSPECIFIED van der Avoird, Ad UNSPECIFIED orcid.org/0000-0003-1856-240X UNSPECIFIED
URN:	urn:nbn:de:hbz:38-686363
DOI:	10.1063/5.0087357
Journal or Publication Title:	J. Chem. Phys.
Volume:	156
Number:	14
Date:	2022
Publisher:	AIP Publishing
Place of Publication:	MELVILLE
ISSN:	1089-7690
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language BASIS-SETS; INFRARED-SPECTRUM; ENERGY-LEVELS; SURFACES; H-3(+); ATOMS; H-3+; EXCITATIONS Multiple languages Chemistry, Physical; Physics, Atomic, Molecular & Chemical Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/68636