Molecular structure calculations: A unified quantum mechanical description of electrons and nuclei using explicitly correlated Gaussian functions and the global vector representation

E. Mat́yus, Markus Reiher

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

We elaborate on the theory for the variational solution of the Schrödinger equation of small atomic and molecular systems without relying on the Born-Oppenheimer paradigm. The all-particle Schrödinger equation is solved in a numerical procedure using the variational principle, Cartesian coordinates, parameterized explicitly correlated Gaussian functions with polynomial prefactors, and the global vector representation. As a result, non-relativistic energy levels and wave functions of few-particle systems can be obtained for various angular momentum, parity, and spin quantum numbers. A stochastic variational optimization of the basis function parameters facilitates the calculation of accurate energies and wave functions for the ground and some excited rotational-(vibrational-)electronic states of H 2 + and H 2, three bound states of the positronium molecule, Ps 2, and the ground and two excited states of the 7Li atom.

Original languageEnglish
Article number024104
JournalThe Journal of Chemical Physics
Volume137
Issue number2
DOIs
Publication statusPublished - Jul 14 2012

Fingerprint

Wave functions
Molecular structure
molecular structure
nuclei
Electrons
Angular momentum
Electronic states
Excited states
Electron energy levels
electrons
Polynomials
wave functions
Atoms
Molecules
Cartesian coordinates
positronium
variational principles
quantum numbers
parity
polynomials

ASJC Scopus subject areas

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

Cite this

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