Adiabatic corrections to density functional theory energies and wave functions.
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 C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT.
Laboratório de Atomos e Moléculas Especiais, Departamento de Física, ICEx, Universidade Federal de Minas Gerais, CP 702, 30123-970, Belo Horizonte, MG, Brasil. rachid@fisica.ufmg.br
José R
JR
Mohallem
Thiago de O
Tde O
Coura
Leonardo G
LG
Diniz
Gustavo
G
de Castro
Denise
D
Assafrão
Thomas
T
Heine