摘要：

Many‐body perturbation theory calculations of the electronic structure are reported forC3vand Jahn–Teller distorted conformations of the methoxy radical CH3O. The Jahn–Teller distortion reduces the energy relative to the minimum energy for theC3vstructure by 0.64 kcal/mol. Furthermore, the dynamic Jahn–Teller effect reduces the calculated spin–orbit splitting from 78 to 37 cm1. An analysis of the Jahn–Teller energy surface yields theemode vibrational frequencies (ν4= 2314, ν5= 1066, ν6= 792 cm1) and Coriolis coupling coefficients (ζ4= 0.065, ζ5= 0.152, and ζ6= 0.186) for the ground state. The orbitalgfactorg0= 0.647 was calculated and used to determine the components of thegtensor for free methoxy and matrix‐trapped methoxy. For free methoxy,g∥= 2.645 andg⊥= 0; for the matrix‐trapped radical, experimental data was used to calculate the splitting 1.7 kcal/mol of the methoxy energy level caused by its site environment. This splitting quenchesg∥to a value of 2.096.

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