Spectroscopic and thermochemical properties of the c-C6H7 radical: a high-level theoretical study

The electronic ground state (X(2)B(1)) of the cyclohexadienyl radical (c-C(6)H(7)) has been studied by explicitly correlated coupled cluster theory at the RCCSD(T)-F12x (x = a, b) level, partly in combination with the double-hybrid density functional method B2PLYP. An accurate equilibrium structure has been established and the ground-state rotational constants are predicted to be A(0) = 5347.3 MHz, B(0) = 5249.7 MHz, and C(0) = 2692.5 MHz. The calculated vibrational wavenumbers agree well with the recent p-H(2) matrix IR data [M. Bahou, Y.-J. Wu, and Y.-P. Lee, J. Chem. Phys. 136, 154304 (2012)] and several predictions have been made. A low value of 6.803 ± 0.005 eV is predicted for the adiabatic ionization energy of c-C(6)H(7). Owing to a moderately large change in the equilibrium structure upon ionization, the first band of the photoelectron spectrum is dominated by the adiabatic peak (100%) and only the peaks corresponding to excitation of the two lowest totally symmetric vibrations (ν(12) and ν(11)) by one vibrational quantum have relative intensities of more than 15%. The C(6)H(6)-H dissociation energy is calculated to be D(0) = 85.7 kJ mol(-1), with an estimated error of ~2 kJ mol(-1).