Document Type

Article

Publication Date

4-25-2013

Abstract

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

First Page

4354

Last Page

4364

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