Density Functional Calculations of E2 and SN2 Reactions: Effects of the Choice of Density Functional, Basis Set, and Self-Consistent Iterations

作者：Zhao, Yan; Truhlar, Donald G.^*

来源：Journal of Chemical Theory and Computation, 2010, 6(4): 1104-1108.

DOI：10.1021/ct100082z

• MAIN-GROUP THERMOCHEMISTRY
• AB-INITIO BENCHMARK
• OXIDATIVE ADDITION
• VALIDATION
• STATES
• PD
• PERFORMANCE
• GAUSSIAN-3
• ENERGIES
• KINETICS

We have computed stationary points on the potential energy surface for the anti-E2, syn-E2, and S(N)2 pathways of the reactions of F- and Cl- with CH3CH2F and CH3CH2Cl with fully self-consistent fields and Gaussian basis functions. We find large differences from previously reported [Bento, A. P.; Sola, M.; Bickelhaupt, F. M. J. Chem. Theory Comput. 2008, 4, 929] calculations with Slater-type orbitals. We revise the findings of the previous study; in particular, we find average absolute errors in kcal/mol compared to benchmark calculations of 20 stationary point energies (6 saddle points and 14 minima) of 0.9 for M06-2X, 1.2 for M08-SO, 1.4 for M06-HF, 2.0 for M06, 2.3 for B3LYP, 2.5 for OLYP, 2.7 for M06-L, and 3.5 kcal/mol for TPSS. We also compare the predictions of various density functionals for the partial atomic charges at the transition states.

• 出版日期2010-4