Adiabatic corrections to density functional theory energies and wave functions

José R. Mohallem, Thiago O. De Coura, Leonardo G. Diniz, Gustavo De Castro, Denise Assafrão, Thomas Heine

Research output: Contribution to journalArticlepeer-review

22 Citations (Scopus)

Abstract

The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes CnH 2n-2W, n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT.

Original languageEnglish
Pages (from-to)8896-8901
Number of pages6
JournalJournal of Physical Chemistry A
Volume112
Issue number38
DOIs
Publication statusPublished - 2008 Sep 25

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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