Willberg, D. M. and Gutmann, M. and Breen, J. J. and Zewail, A. H. (1992) Real-time dynamics of clusters. I. I_2X_n(n=1). Journal of Chemical Physics, 96 (1). pp. 198-212. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20120330-073046238
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Vibrational predissociation of I_2X_n (X=Ne, Ar) van der Waals clusters are studied in real‐time using picosecond pump–probe (LIF) and molecular beam techniques. The state‐to‐state rates of vibrational predissociation are measured for specific vibrational levels v′_i by monitoring the rise of nascent I_2. Here, we report our study of I_2X(B,v′_i)k(v '_i,v′_f) →I_2(B,v′_f)+X. For I_2Ne, the values of τ=k^(−1)(v'_i,v′_f) decrease nonlinearly from 216 ps for v'_i=13 to 53 ps for v′_i=23. For I_2Ar (B,v'_i), which undergo electronic and vibrational predissociation, the risetime of the nascent I_2 is found to be 70 ps when v′_i=18 and 77 ps when v'_i=21. A number of theoretical models for vibrational predissociation (the energy‐gap law, the momentum‐gap law, quantum and classical calculations) are compared with our experimental results in an attempt to understand the key features of the dynamics and the potential energy surface.
|Additional Information:||© 1991 American Institute of Physics. Received 16 August 1991; accepted 19 September 1991. This work was supported by a grant from the National Science Foundation (DMR). L. W. Peng and P. Cong contributed to the construction of the laboratory apparatus described in the earlier communication and in this paper. We are grateful to their help and the many discussions we had with them. We have also enjoyed discussions with Professor E. E. Nikitin and Professor J. A. Beswick during their visits to Caltech, and with Professor G. Delgado-Barrio on some.|
|Subject Keywords:||VIBRATIONAL STATES, PREDISSOCIATION, VAN DER WAALS FORCES, ATOMIC CLUSTERS, NEON, ARGON, REAL TIME SYSTEMS, PS RANGE, MOLECULAR BEAMS, NONLINEAR PROBLEMS, POTENTIAL ENERGY SURFACES|
|Classification Code:||PACS: 36.40.-c; 33.80.Gj; 33.15.Hp; 34.50.-s|
|Official Citation:||Real‐time dynamics of clusters. I. I2Xn (n=1) D. M. Willberg, M. Gutmann, J. J. Breen, and A. H. Zewail J. Chem. Phys. 96, 198 (1992); http://dx.doi.org/10.1063/1.462499|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||30 Mar 2012 15:44|
|Last Modified:||18 Aug 2016 23:08|
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