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Density functional theory(DFT) and Hartree-Fock(HF) calculations are reportedfor the family of transition metal fluorides $\mbox{ScF}_3$, $\mbox{TiF}_4$,$\mbox{VF}_5$, and $\mbox{CrF}_6$. Both HF and the local-density-aproximation(LDA) yield excellent agreement with experimental bond lengths, while the B-LYPgradient-corrected density functional gives bond lengths $0.04-0.05$ \AA\ toolong. An investigation of various combinations of exchange and correlationfunctionals shows that, for this series, the origin of this behavior lies inthe Becke exchange functional. Much improved bond distances are found using thehybrid HF/DFT functional advocated by Becke. This approximation also leads tomuch improved thermochemistries. The LDA overestimates average bond energies inthis series by $30-40$ kcal/mol, whereas the B-LYP functional overbinds by only$\sim8-12$ kcal/mol, and the hybrid HF/DFT method overbinds by only $\sim 2$kcal/mol. The hybrid method predicts the octahedral isomer of $\mbox{CrF}_6$ tobe more stable than the trigonal prismatic form by $14$ kcal/mol. Comparison oftheoretical vibrational frequencies with experiment supports the assignment ofan octahedral geometry.Comment: 18 pages, latex, 1 figure, Submitted to Journal of Chemical Physic

Application of gradient-corrected density functional theory to the structures and thermochemistries of ScF3, TiF4, VF5, and CrF6