Laser cooling of internal molecular degrees of freedom for vibrationally hot molecules

We present an approach to laser cooling of internal molecular degrees of freedom for vibrationally hot molecules using a sequence of ultrashort laser pulses. It is assumed that the molecules initially occupy different vibrational states with a substantial portion of the molecules being in excited vibrational states. We show that the ultimate aim of increasing the vibrational ground-state population through a reduction of the system's entropy can be achieved through a multistep process. In the first step, we design an ultrashort laser pulse that selectively transfers most of the population of the excited vibrational states to an excited electronic surface; then the field is switched off and the system allowed to relax until most of the excited electronic state population has decayed due to spontaneous emission. By repeating this procedure a few times, the entropy of the system can be substantially reduced and the population of the vibrational ground state increased considerably, even if the lifetimes of the excited electronic states are much greater than the length of a control pulse, i.e., if dissipative effects are negligiable on the time scales of coherent control.