TY - JOUR
T1 - Comparative study of identity proton-transfer reactions between simple atoms or groups by VB methods
AU - Wu, Wei
AU - Shaik, Sason
AU - Saunders, William H.
PY - 2002/11/28
Y1 - 2002/11/28
N2 - Valence bond SCF calculations have been carried out on identity proton transfers of the type X-H + X- → X- + H-X and X-H+ + X → X + X-H+ for systems where X = F-, Cl-, Br-, OH-, SH-, NH2-, PH2-, CH3-, SiH3-, OH2, NH3, and PH3. A hybrid consisting of three contributing structures-reactantlike, productlike, and ionic (X- H+ X- or X H+ X)-gives reasonable results, though additional structures afford a slight further decrease in energy. Energies somewhat below Hartree-Fock and reasonable weights are obtained. Calculated barriers agree well with those obtained by high-level ab initio calculations with correlation. Insights into the factors determining barrier height are obtained.
AB - Valence bond SCF calculations have been carried out on identity proton transfers of the type X-H + X- → X- + H-X and X-H+ + X → X + X-H+ for systems where X = F-, Cl-, Br-, OH-, SH-, NH2-, PH2-, CH3-, SiH3-, OH2, NH3, and PH3. A hybrid consisting of three contributing structures-reactantlike, productlike, and ionic (X- H+ X- or X H+ X)-gives reasonable results, though additional structures afford a slight further decrease in energy. Energies somewhat below Hartree-Fock and reasonable weights are obtained. Calculated barriers agree well with those obtained by high-level ab initio calculations with correlation. Insights into the factors determining barrier height are obtained.
UR - http://www.scopus.com/inward/record.url?scp=0037191798&partnerID=8YFLogxK
U2 - 10.1021/jp021452w
DO - 10.1021/jp021452w
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AN - SCOPUS:0037191798
SN - 1089-5639
VL - 106
SP - 11616
EP - 11622
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 47
ER -