Multireference configuration interaction (MRCI) calculations of the lowest singlet X (1A'), triplet � (3A�) and the first excited singlet � (1A�) states have been performed for a series of iodocarbenes: CHI, CFI, CClI, CBrI, and CI2. The MRCI calculations were performed with augmented correlation consistent basis sets of valence triple zeta plus polarization quality (aug-cc-pVTZ), employing a full-valence active space of 18 electrons in 12 orbitals (12 and 9, respectively for CHI). Results obtained include equilibrium geometries and harmonic vibrational frequencies for each of the electronic states, along with � (3A�) ? X (1A') singlet-triplet gaps and � (1A�) ? X (1A') transition energies, both including zero-point vibrational energy corrections. Additionally, potential energy surface (PES) cuts along the carbon-iodine bond of the lowest singlet X (1A'), triplet � (3A�) and the first excited singlet � (1A�) states of each species were investigated at the MRCI/aug-cc-pVTZ level. The PES studies provide an examination of dissociative behavior for this series of iodocarbenes along with investigations of barriers to exit channels due to possible multiple state interactions. 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 iodocarbenes.

High level quantum mechanical studies of iodocarbenes

243rd National Meeting (2012)

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