Doubly vibrationally enhanced four-wave mixing in crotononitrile.

Doubly vibrationally enhanced (DOVE) resonances have been observed in the infrared four-wave mixing (IRFWM) spectra of crotononitrile. The 2D DOVE-FWM spectra of the cis and trans isomers of crotononitrile showed cross peaks between the CN stretching fundamental and the CN + C=C stretch and the CN + C-C stretch combination bands for each of the two isomers that were observed, demonstrating the isomer selectivity of DOVE-IRFWM. Frequency-domain simulations were able to reproduce the features of the observed spectra, so the values for the nonlinearity and dephasing rates of all of the nonlinear processes could be measured. The results are compared to the calculations of the third-order susceptibility based on the transition moments, line positions, and line widths observed in the infrared absorption and the Raman spectra of crotononitrile.