Nonadiabatic rotational states of the hydrogen molecule

We present a new computational method for the determination of energy levels in four-particle systems like H 2 , HD, and HeH + using explicitly correlated exponential basis functions and analytic integration formulas. In solving the Schrödinger equation, no adiabatic separation of the nuclear and el...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2017-12, Vol.2 (1), p.247-255
Main Authors: Pachucki, Krzysztof, Komasa, Jacek
Format: Article
Language:English
Subjects:
Adiabatic flow
Basis functions
Correlation analysis
Energy levels
Mathematical analysis
Rotational states
Schrodinger equation
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Summary:We present a new computational method for the determination of energy levels in four-particle systems like H 2 , HD, and HeH + using explicitly correlated exponential basis functions and analytic integration formulas. In solving the Schrödinger equation, no adiabatic separation of the nuclear and electronic degrees of freedom is introduced. We provide formulas for the coupling between the rotational and electronic angular momenta, which enable calculations of arbitrary rotationally excited energy levels. To illustrate the high numerical efficiency of the method, we present the results for various states of the hydrogen molecule. The relative accuracy to which we determined the nonrelativistic energy reached the level of 10 −12 -10 −13 , which corresponds to an uncertainty of 10 −7 -10 −8 cm −1 . A new method of solving the Schrödinger equation to a high accuracy for a four-body system with Coulomb interactions using exponential wave functions.
ISSN:1463-9076
1463-9084
DOI:10.1039/c7cp06516g