Vibrational relaxation dynamics of SD molecules in As2S3: Observation of an anomalous isotope effect

It is generally assumed that the vibrational relaxation of molecular impurities in crystals and glasses mainly depends on the order of the decay process, with lower order processes leading to more rapid relaxation (a behavior that is known under the term open-quotes gap-lawclose quotes). Here we present measurements that contradict this assumption. Using high intensity psec pulses of the Stanford FEL we measured the relaxation rate of the SD vibrational stretch mode (at a frequency of 1800 cm) by applying a pump-probe technique. We find relaxation rates on the order of 2x109 sec-1, which are a factor of 2 lower than those found for the isotope molecule SH (at a frequency of about 2500 cm-1) in the same host1. We recall that the relaxation of the SD vibrational stretch mode is controlled by a lower order process as compared to the SH molecule, which is due to the smaller number of host vibrational quanta to match the energy of the stretch mode; a fact we have confirmed experimentally by temperature dependent relaxation measurements. Thus our remits are in marked contrast to the so-called open-quotes Gap-Lawclose quotes and emphasize the importance of the molecule - host coupling in the relaxation dynamics