Orbital Following in the Methyl Radical

摘要: Incomplete orbital following of the molecular vibrations in methyl radical is examined through its relationship to hyperfine splittings observed ESR spectrum. A semiempirical nonionic valence‐bond theory with different degrees carbon sigma‐orbital used estimate proton and C13 splitting constants as a function nuclear positions that correspond out‐of‐plane bending mode. It found considerable ``lag'' motion respect nuclei required achieve consistent interpretation spectrum isotopic analogs. variety additional factors (i.e., integral parameter variation, breakdown Born—Oppenheimer approximation, ionic contributions, other vibrations) are also investigated determine their effects on splittings. Although some be significant (particularly choice parameters), it appears they cannot serve to...