The standard enthalpy of formation of CH2

Abstract

High-quality ab initio quantum chemical methods, including higher-order coupled cluster and full configuration interaction benchmarks, with basis sets ranging from [C/H] [4s3p1d/2s1p] to [9s8p7d5f4g3h2i/7s6p5d4f3g2h] have been employed to obtain the best technically possible value for the standard enthalpy of formation of X̃ 3B1 CH2 and ã 1A1 CH2. Careful extrapolations of finite basis MP2, CCSD, CCSD(T), and CCSDT energies to the complete basis set full configuration interaction limit plus inclusion of small corrections owing to relativistic effects, core correlation, and the diagonal Born–Oppenheimer correction results in the final extrapolated enthalpies of formation of this study, ΔfH0o(X̃ 3B1 CH2)=390.45−0.64+0.68 kJ mol−1 and ΔfH0o(ã 1A1 CH2)=428.10−0.64+0.68 kJ mol−1. The computed value for X̃ 3B1 CH2 is in between the best two experimental results of 389.87±0.86 and 390.73±0.66 kJ mol−1. The elaborate calculations leading to these enthalpies of formation also resulted in accurate estimates of the singlet-triplet splitting, T0(ã 1A1 CH2)=37.54−0.29+0.41 kJ mol−1, in excellent agreement with the best empirical value of 37.65±0.06 kJ mol−1, of the total atomization enthalpy, D0(X̃ 3B1 CH2)=753.03−0.62+0.43 kJ mol−1, in excellent agreement with the best experimental value of 753.3 kJ mol−1, of the bond dissociation energy, DU1o(0 K)(CH–H)=417.85±0.35 kJ mol−1, and of the quartic force field representations of the potentials of the two states around their respective minima.