Non-Born-Oppenheimer calculations of atoms and molecules

Mauricio Cafiero, Sergiy Bubin, Ludwik Adamowicz

Research output: Contribution to journalArticle

127 Citations (Scopus)

Abstract

We review a recent development in high-accuracy non-Born-Oppenheimer calculations of atomic and molecular systems in a basis of explicitly correlated Gaussian functions. Much of the recent progress in this area is due to the derivation and implementation of analytical gradients of the energy functional with respect to variational linear and non-linear parameters of the basis functions. This method has been used to obtain atomic and molecular ground and excited state energies and the corresponding wave functions with accuracy that exceeds previous calculations. Further, we have performed the first calculations of non-linear electrical properties of molecules without the Born-Oppenheimer approximation for systems with more than one electron. The results for the dipole moments of such systems as HD and LiH agree very well with experiment. After reviewing our non-Born-Oppenheimer results we will discuss ways this method can be extended to deal with larger molecular systems with and without an external perturbation.

Original languageEnglish
Pages (from-to)1491-1501
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume5
Issue number8
DOIs
Publication statusPublished - Apr 15 2003
Externally publishedYes

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Atoms
Molecules
atoms
Born approximation
molecules
Born-Oppenheimer approximation
reviewing
Dipole moment
Wave functions
Excited states
Ground state
Electric properties
dipole moments
derivation
electrical properties
wave functions
perturbation
gradients
ground state
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Atomic and Molecular Physics, and Optics

Cite this

Non-Born-Oppenheimer calculations of atoms and molecules. / Cafiero, Mauricio; Bubin, Sergiy; Adamowicz, Ludwik.

In: Physical Chemistry Chemical Physics, Vol. 5, No. 8, 15.04.2003, p. 1491-1501.

Research output: Contribution to journalArticle

Cafiero, Mauricio ; Bubin, Sergiy ; Adamowicz, Ludwik. / Non-Born-Oppenheimer calculations of atoms and molecules. In: Physical Chemistry Chemical Physics. 2003 ; Vol. 5, No. 8. pp. 1491-1501.
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