Abstract
B 2A‘(3p) ← X 2A‘‘ spectra of the isotopically substituted hydroxymethyl radicals (CH2OH, CH2OD, CD2OH, CD2OD) were observed between 39 700 and 43 000 cm-1 by 2+1, 2+2, and 1+1 resonance-enhanced multiphoton ionization (REMPI) spectroscopy. Analyses of the vibrational hot bands in these spectra show that the ν8 torsion modes and ν9 CH2-wag mode are strongly coupled and governed by nonharmonic potential energy functions; for example, for 12CH216OH(X 2A‘‘) we obtain 2ν8 = 846 ± 6 cm-1(1σ), 1ν9 = 234 ± 5 cm-1, and 2ν9 = 615 ± 6 cm-1. Using MP2/6-311G(2df,2p) ab initio calculations, we constructed the two-dimensional potential energy surfaces that govern the ν8 torsion modes and ν9 CH2-wag in the X 2A‘‘ radical and the X 1A‘ cation core of the B 2A‘(3p) Rydberg state. Energy levels calculated with these potential energy surfaces account for the REMPI bands originating from the ν8 hindered rotor and the ν9 CH2-wag modes. The experimental and ab initio results lead to improved heat capacities and entropie...
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