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Title: Vibrational relaxation dynamics of SD molecules in As{sub 2}S{sub 3}: Observation of an anomalous isotope effect

Conference ·
OSTI ID:238872
;  [1];  [2]
  1. Univ. of Georgia, Athens, GA (United States)
  2. Stanford Univ., CA (United States); and others

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-law{close_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 2x10{sup 9} sec{sup -1}, which are a factor of 2 lower than those found for the isotope molecule SH (at a frequency of about 2500 cm{sup - 1}) in the same host{sup 1}. 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-Law{close_quotes} and emphasize the importance of the molecule - host coupling in the relaxation dynamics.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
OSTI ID:
238872
Report Number(s):
BNL-61982-Absts.; CONF-9508156-Absts.; ON: DE96002729; CNN: Grant N00014-94-1-1024; TRN: 96:013362
Resource Relation:
Conference: 17. international free electron laser conference, New York, NY (United States), 21-25 Aug 1995; Other Information: PBD: [1995]; Related Information: Is Part Of 17th international free electron laser conference and 2nd international FEL users` workshop. Program and abstracts; PB: 300 p.
Country of Publication:
United States
Language:
English

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