Journal of Physical Chemistry A, Vol.115, No.7, 1243-1249, 2011
Multireference Configuration Interaction Study of Bromocarbenes
Multireference configuration interaction (MRCI) calculations of the lowest singlet (X) over tilde (1A') and triplet (a) over tilde((3)A '') states as well as the first excited singlet (A) over tilde((1)A '') state have been performed for a series of bromocarbenes: CHBr, CFBr, CClBr, CBr2, and CIBr. The MRCI calculations were performed with correlation consistent basis sets of valence triple-zeta plus polarization quality, employing a full-valence active space of 18 electrons in 12 orbitals (12 and 9, respectively, for CHBr). Results obtained include equilibrium geometries and harmonic vibrational frequencies for each of the electronic states, along with (a) over tilde((3)A '') -> (X) over tilde((1)A') singlet-triplet gaps and (A) over tilde((1)A '') <- (X) over tilde((1)A') transition energies. Comparisons have been made with previous computational and experimental results where available. The MRCI calculations presented in this work provide a comprehensive series of results at a consistent high level of theory for all of the bromocarbenes.