Premium
Density functional Gaussian‐type orbital approach in theoretical study of S 2 F 2 isomerization
Author(s) -
Jursic Branko S.
Publication year - 1996
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(199605)17:7<835::aid-jcc7>3.0.co;2-t
Subject(s) - isomerization , basis set , density functional theory , hybrid functional , gaussian , basis (linear algebra) , chemistry , computational chemistry , molecular physics , atomic physics , physics , mathematics , geometry , catalysis , biochemistry
The structures of two isomers, difluorodisulfane (FSSF) and thiothionylfluoride(SSF 2 ), and the corresponding transition structure were generated withdensity functional theory (DFT) methods. Three groups of DFT methods were used: local(Local Spin Density Approximation, LSDA), nonlocal (local with gradient corrections;BLYP and BP86), and hybrid methods that include a mixture of Hartree‐Fock (HF) exchangewith nonlocal correlation (Becke3BLYP, Becke3P86). An extended basis set [6‐311 + +G(3 df )] was used for all calculations, although satisfactory results can beobtained with the 6‐311G( d ) basis set. The geometries obtained were comparedwith both restricted Hartree‐Fock (RHF) calculated and experimentally obtained values.The energy outcome and the activation barrier for the isomerization were evaluated. Itwas determined that excellent geometries can be obtained with the Becke3B86 hybridmethod, whereas for reasonable energies MP2 single‐point calculations on thesegeometries are necessary. © 1996 by John Wiley & Sons, Inc.