Calibration-quality adiabatic potential energy surfaces for H 3 + and its isotopologues

Michele Pavanello, Ludwik Adamowicz, Alexander Alijah, Nikolai F. Zobov, Irina I. Mizus, Oleg L. Polyansky, Jonathan Tennyson, Tamás Szidarovszky, A. Császár

Research output: Contribution to journalArticle

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Abstract

Calibration-quality ab initio adiabatic potential energy surfaces (PES) have been determined for all isotopologues of the molecular ion H3+. The underlying Born-Oppenheimer electronic structure computations used optimized explicitly correlated shifted Gaussian functions. The surfaces include diagonal Born-Oppenheimer corrections computed from the accurate electronic wave functions. A fit to the 41 655 ab initio points is presented which gives a standard deviation better than 0.1cm -1 when restricted to the points up to 6000cm -1 above the first dissociation asymptote. Nuclear motion calculations utilizing this PES, called GLH3P, and an exact kinetic energy operator given in orthogonal internal coordinates are presented. The ro-vibrational transition frequencies for H3+, H 2D, and HD2+ are compared with high resolution measurements. The most sophisticated and complete procedure employed to compute ro-vibrational energy levels, which makes explicit allowance for the inclusion of non-adiabatic effects, reproduces all the known ro-vibrational levels of the H3+ isotopologues considered to better than 0.2cm -1. This represents a significant (order-of-magnitude) improvement compared to previous studies of transitions in the visible. Careful treatment of linear geometries is important for high frequency transitions and leads to new assignments for some of the previously observed lines. Prospects for further investigations of non-adiabatic effects in the H3+ isotopologues are discussed. In short, the paper presents (a) an extremely accurate global potential energy surface of H3+ resulting from high accuracy ab initio computations and global fit, (b) very accurate nuclear motion calculations of all available experimental line data up to 16 000cm -1, and (c) results suggest that we can predict accurately the lines of H3+ towards dissociation and thus facilitate their experimental observation.

Original languageEnglish
Article number184303
JournalThe Journal of Chemical Physics
Volume136
Issue number18
DOIs
Publication statusPublished - May 14 2012

Fingerprint

Potential energy surfaces
potential energy
Calibration
dissociation
asymptotes
Wave functions
allowances
molecular ions
Kinetic energy
Electron energy levels
Electronic structure
standard deviation
kinetic energy
energy levels
wave functions
inclusions
Ions
electronic structure
operators
Geometry

ASJC Scopus subject areas

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

Cite this

Pavanello, M., Adamowicz, L., Alijah, A., Zobov, N. F., Mizus, I. I., Polyansky, O. L., ... Császár, A. (2012). Calibration-quality adiabatic potential energy surfaces for H 3 + and its isotopologues. The Journal of Chemical Physics, 136(18), [184303]. https://doi.org/10.1063/1.4711756

Calibration-quality adiabatic potential energy surfaces for H 3 + and its isotopologues. / Pavanello, Michele; Adamowicz, Ludwik; Alijah, Alexander; Zobov, Nikolai F.; Mizus, Irina I.; Polyansky, Oleg L.; Tennyson, Jonathan; Szidarovszky, Tamás; Császár, A.

In: The Journal of Chemical Physics, Vol. 136, No. 18, 184303, 14.05.2012.

Research output: Contribution to journalArticle

Pavanello, M, Adamowicz, L, Alijah, A, Zobov, NF, Mizus, II, Polyansky, OL, Tennyson, J, Szidarovszky, T & Császár, A 2012, 'Calibration-quality adiabatic potential energy surfaces for H 3 + and its isotopologues', The Journal of Chemical Physics, vol. 136, no. 18, 184303. https://doi.org/10.1063/1.4711756
Pavanello M, Adamowicz L, Alijah A, Zobov NF, Mizus II, Polyansky OL et al. Calibration-quality adiabatic potential energy surfaces for H 3 + and its isotopologues. The Journal of Chemical Physics. 2012 May 14;136(18). 184303. https://doi.org/10.1063/1.4711756
Pavanello, Michele ; Adamowicz, Ludwik ; Alijah, Alexander ; Zobov, Nikolai F. ; Mizus, Irina I. ; Polyansky, Oleg L. ; Tennyson, Jonathan ; Szidarovszky, Tamás ; Császár, A. / Calibration-quality adiabatic potential energy surfaces for H 3 + and its isotopologues. In: The Journal of Chemical Physics. 2012 ; Vol. 136, No. 18.
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