Differential hydration of tricyanomethanide observed by time resolved vibrational spectroscopy
The degenerate transition corresponding to asymmetric stretches of the D3h tricyanomethanide anion, C(CN)3-, in aqueous solution was investigated by linear FTIR spectroscopy, femtosecond pump-probe spectroscopy, and 2D IR spectroscopy. Time resolved vibrational spectroscopy shows that water induces vibrational energy transfer between the degenerate asymmetric stretch modes of tricyanomethanide. The frequency-frequency correlation function and the vibrational energy transfer show two significantly different ultrafast time scales. The system is modeled with molecular dynamics simulations and ab initio calculations. A new model for theoretically describing the vibrational dynamics of a degenerate transition is presented. Microscopic models, where water interacts axially and radially with the ion, are suggested for the transition dipole reorientation mechanism. © 2012 American Chemical Society.
Publication Source (Journal or Book title)
Journal of Physical Chemistry B
Kuroda, D., Singh, P., & Hochstrasser, R. (2013). Differential hydration of tricyanomethanide observed by time resolved vibrational spectroscopy. Journal of Physical Chemistry B, 117 (16), 4354-4364. https://doi.org/10.1021/jp3069333