Vibrational dynamics of tricyanomethanide

Steady-state and time resolved IR spectroscopy have been used to characterize vibrational spectra and relaxation dynamics of the antisymmetric CN stretching band of tricyanomethanide (TCM) in solutions of water, heavy water, methanol, dimethyl sulfoxide, formamide, and the ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4]. The vibrational energy relaxation times for tricyanomethanide in these solvents are longer than those previously reported for dicyanamide, another CN containing anion, in the same solvents. Results of ab initio calculations of the vibrational frequencies for tricyanomethanide depend on the method used and compare favorably with experimentally measured values for IR-active and Raman-active bands. Proton and electron affinities were also calculated.