Journal of Chemical Physics, Vol.115, No.5, 2267-2281, 2001
Nonequilibrium initial conditions of a Brownian oscillator system observed by two-dimensional spectroscopy
We study effects of a nonequilibrium initial condition of a Brownian oscillator system upon two-, three-, and four-time correlation functions of an oscillator coordinate as a subject of multidimensional spectroscopy. A nonequilibrium initial condition is set by a displacement of a Gaussian wave packet in an oscillator potential. Such situation may be found in a vibrational motion of molecules after a sudden bond breaking between a fragmental molecule and a targeting vibrational system or a movement of wave packet in an electronic excited state potential surface created by a laser pump pulse. Multitime correlation functions of oscillator coordinates for a nonequilibrium initial condition are calculated analytically with the use of generating functional from a path integral approach. Two-, three-, and four-time correlation functions of oscillator coordinates correspond to the third-, fifth-, and seventh-order Raman signals or the first-, second-, and third-order infrared signals. We plotted these correlation functions as a signal in multidimensional spectroscopy. The profile of the signal depends on the initial position and momentum of the wave packet in the fifth- and seventh-order Raman or the second and third order infrared measurement, which makes it possible to measure the dynamics of the wave packet directly in the phase space by optical means.