TY - JOUR
T1 - Valence bond modeling of barriers in the nonidentity hydrogen abstraction reactions, X′· + H-X → X′-H + X· (X′ ≠ X = CH3, SiH3, GeH3, SnH3, PbH3)
AU - Song, Lingchun
AU - Wu, Wei
AU - Dong, Kunming
AU - Hiberty, Philippe C.
AU - Shaik, Sason
PY - 2002/11/21
Y1 - 2002/11/21
N2 - Breathing orbital valence bond (BOVB) computations (Hiberty, P.C.; Humbel, S.; Byrman, C.P.; van Lenthe, J.H. J. Chem. Phys. 1994, 101, 5969) are used to obtain nonidentity barriers for hydrogen transfer reactions between X and X′ groups, X ≠ X′ = CH3; SiH3, GeH3, SnH3, PbH3. Modeling of these barriers by means of VB state correlation diagrams (Shaik, S.; Shurki, A. Angew. Chem., Int. Ed. Engl. 1999, 38, 586) leads to a simple expression for the barrier (eq 29) as an interplay of an intrinsic term and the reaction driving force. The equation predicts barrier heights that are compatible with the BOVB computed barrier heights. Its comparison with the Marcus equation shows similarities and differences.
AB - Breathing orbital valence bond (BOVB) computations (Hiberty, P.C.; Humbel, S.; Byrman, C.P.; van Lenthe, J.H. J. Chem. Phys. 1994, 101, 5969) are used to obtain nonidentity barriers for hydrogen transfer reactions between X and X′ groups, X ≠ X′ = CH3; SiH3, GeH3, SnH3, PbH3. Modeling of these barriers by means of VB state correlation diagrams (Shaik, S.; Shurki, A. Angew. Chem., Int. Ed. Engl. 1999, 38, 586) leads to a simple expression for the barrier (eq 29) as an interplay of an intrinsic term and the reaction driving force. The equation predicts barrier heights that are compatible with the BOVB computed barrier heights. Its comparison with the Marcus equation shows similarities and differences.
UR - http://www.scopus.com/inward/record.url?scp=0037153314&partnerID=8YFLogxK
U2 - 10.1021/jp026438y
DO - 10.1021/jp026438y
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AN - SCOPUS:0037153314
SN - 1089-5639
VL - 106
SP - 11361
EP - 11370
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 46
ER -