An accurate barrier for the hydrogen exchange reaction from valence bond theory: Is this theory coming of age?
- 化学化工－已发表论文 
One of the landmark achievements of quantum chemistry, specifically of MO-based methods that include electron correlation, was the precise calculation of the barrier for the hydrogen-exchange reaction (B. Liu, J. Chem. Phys. 1973, 58, 1925; P. Siegbahn, B. Liu, J. Chem. Phys. 1978, 68, 2457). This paper reports an accurate calculation of this barrier by two recently developed VB methods that use only the eight classical VB structures. To our knowledge, the present work is the first accurate ab initio, VB barrier that matches an experimental value. Along with the accurate barrier, the VB method provides accurate bond energies and diabatic quantities that enable the barrier height to be analyzed by the VB state correlation diagram approach, VBSCD (S. Shaik, A. Shurki, Angew. Chem. 1999, 111, 616; Angew. Chem. Int. Ed. Engl. 1999, 38, 586). This is a proof of principal that VB theory with appropriate account of dynamic electron correlation can achieve quantitative. accuracy of reaction barriers, and still retain a compact and interpretable wave function. A sample Of S(N)2 barriers and dihalogen bonding energies, which are close to CCSD(T) and G2(+) values, show that the H-3 problem is not an isolated case, and while it is premature to conclude that VB theory has come of age, the occurrence of this event is clearly within sight.