TY - JOUR
T1 - Quantitative valence bond computation of a curve crossing diagram for a model SN2 reaction, H- + CH3H′ → HCH3 + H′-
AU - Sini, Gjergji
AU - Shaik, Sason S.
AU - Lefour, Jean Michel
AU - Ohanessian, Gilles
AU - Hiberty, Philippe C.
PY - 1989
Y1 - 1989
N2 - A quantitative avoided crossing diagram for the model SN2 reaction, Hl- + CH3Hr. → HlCH3 + Hr-, is computed by using a VB method based on local fragment orbitals. The essential parameters of curves are quantified at the 6-31G*+D level. The vertical electron-transfer energy gap, G, is 174 kcal/mol. The height of the crossing point (relative to H- + CH4) is 42% of G. The quantum mechanical resonance energy of the transition state, i.e., the avoided crossing interaction, is 15.9 kcal/mol. The barrier of 56.8 kcal/mol is computed as the difference between the height of the crossing point and the avoided crossing interaction. All these parameters show insignificant basis set dependence and support previous estimations of these parameters which formed the crucial hypotheses for the use of the avoided crossing model to discuss reactivity trends.
AB - A quantitative avoided crossing diagram for the model SN2 reaction, Hl- + CH3Hr. → HlCH3 + Hr-, is computed by using a VB method based on local fragment orbitals. The essential parameters of curves are quantified at the 6-31G*+D level. The vertical electron-transfer energy gap, G, is 174 kcal/mol. The height of the crossing point (relative to H- + CH4) is 42% of G. The quantum mechanical resonance energy of the transition state, i.e., the avoided crossing interaction, is 15.9 kcal/mol. The barrier of 56.8 kcal/mol is computed as the difference between the height of the crossing point and the avoided crossing interaction. All these parameters show insignificant basis set dependence and support previous estimations of these parameters which formed the crucial hypotheses for the use of the avoided crossing model to discuss reactivity trends.
UR - http://www.scopus.com/inward/record.url?scp=0001716811&partnerID=8YFLogxK
U2 - 10.1021/j100352a007
DO - 10.1021/j100352a007
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AN - SCOPUS:0001716811
SN - 0022-3654
VL - 93
SP - 5661
EP - 5665
JO - Journal of Physical Chemistry
JF - Journal of Physical Chemistry
IS - 15
ER -