Journal of Chemical Physics, Vol.111, No.22, 10046-10052, 1999
Energetic and structural features of the CH4+O(P-3)-> CH3+OH abstraction reaction: Does perturbation theory from a multiconfiguration reference state (finally) provide a balanced treatment of transition states?
The stationary points of the CH4+O(P-3)--> CH3+OH abstraction reaction have been identified at the fully optimized reaction space (FORS) level. For three sets of geometries (FORS plus unrestricted and restricted-open-shell Moller-Plesset second order perturbation theory), single-point calculations by unrestricted Moller-Plesset fourth order perturbation theory (UMP4), by unrestricted coupled cluster theory with single and double excitations and a quasiperturbative treatment of fourth-and fifth-order triple-excitation terms (CCDS(T)), and by multireference Moller-Plesset second order perturbation theory (MRMP2) were also performed for the classical barrier height and energy of the reaction. Calculations carried out at the MRMP2/cc-pVTZ//FORS/cc-pVTZ level predict values for the forward vibrationally adiabatic barrier height and for the energy of the reaction at 0 K equal to 10.3 and 2.0 kcal/mol, respectively. This is in excellent agreement with experiments that show values of the activation energies in the range of 9-12 kcal/mol (at temperatures below 1500 K) and an energy of reaction equal to 1.8 kcal/mol. Expectation values of (S) over cap(2), where (S) over cap is total electron spin, and also the values the coefficients of the configuration state functions show that the reactants and the products of this reaction are well described by single-configuration reference states but that the transition structure has a much higher multiconfigurational character. We conclude that MRMP2 may provide some light at the end of the tunnel in the long-standing quest for method that includes nondynamical and dynamical correlation in a balanced way in the electronic wave function of open-shell transition states.