Non-Born-Oppenheimer method for direct variational calculations of diatomic first excited rotational states using explicitly correlated all-particle Gaussian functions

Keeper L. Sharkey, Nikita Kirnosov, Ludwik Adamowicz

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

We report the development of a direct variational method for calculating the first rotational excited state of diatomic molecules with σ electrons where the Born-Oppenheimer approximation is not assumed. The method employs all-particle explicitly correlated Gaussian basis functions. The exponential parameters of the Gaussians are optimized with the aid of an analytically calculated energy gradient determined with respect to these parameters. The method is tested in calculations of the ortho-para spin isomerization of the hydrogen molecule in its all-bound vibrational states.

Original languageEnglish (US)
Article number032513
JournalPhysical Review A
Volume88
Issue number3
DOIs
StatePublished - Sep 20 2013

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rotational states
Born-Oppenheimer approximation
diatomic molecules
vibrational states
isomerization
gradients
hydrogen
excitation
molecules
electrons
energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

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abstract = "We report the development of a direct variational method for calculating the first rotational excited state of diatomic molecules with σ electrons where the Born-Oppenheimer approximation is not assumed. The method employs all-particle explicitly correlated Gaussian basis functions. The exponential parameters of the Gaussians are optimized with the aid of an analytically calculated energy gradient determined with respect to these parameters. The method is tested in calculations of the ortho-para spin isomerization of the hydrogen molecule in its all-bound vibrational states.",
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AB - We report the development of a direct variational method for calculating the first rotational excited state of diatomic molecules with σ electrons where the Born-Oppenheimer approximation is not assumed. The method employs all-particle explicitly correlated Gaussian basis functions. The exponential parameters of the Gaussians are optimized with the aid of an analytically calculated energy gradient determined with respect to these parameters. The method is tested in calculations of the ortho-para spin isomerization of the hydrogen molecule in its all-bound vibrational states.

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