Time evolution of reactants, intermediates, and products in the vibrational predissociation of Br2•••Ne:: A theoretical study

被引:28
作者
Miguel, B [1 ]
Bastida, A
Zúñiga, J
Requena, A
Halberstadt, N
机构
[1] Univ Murcia, Dept Quim Fis, E-30100 Murcia, Spain
[2] Univ Toulouse 3, IRSAMC, F-31062 Toulouse, France
[3] CNRS, F-31062 Toulouse, France
关键词
D O I
10.1063/1.1323506
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A hybrid quantum/classical simulation of the vibrational predissociation of the Br-2. . . Ne cluster in the B state is carried out. The resulting lifetimes and final rovibrational state distributions compare very well with the experimental measurements, as well as with accurate quantum mechanical results. The time-evolution of the reactants, products, and intermediates is analyzed by a kinetic mechanism, comporting three elementary steps: direct vibrational predissociation (VP), intramolecular vibrational redistribution (IVR), and evaporative cooling (EC). The importance of intramolecular vibrational redistribution followed by evaporative cooling relative to direct vibrational predissociation is shown to evolve from 100% of VP for the lowest initial vibrational level v=10 to 53% for the highest one v=27. In the cases where IVR is important, the complexes are shown to explore the whole configuration space, in contrast with the cases where dynamics are governed by direct vibrational predissociation for which the complexes mainly evolve in the region around the T-shaped equilibrium configuration. A time-dependent picosecond experiment is proposed to detect the IVR intermediates, based on their different structure. It consists of exciting the complex with a first laser and probing the intermediates with a second laser to an electronic state with a minimum in the collinear configuration where the initially excited state wave function has no weight. The ground state of the positive ion is proposed as the final state, so that ions are detected. An appreciable population of intermediates is predicted for initial excited levels with v greater than or equal to 20. (C) 2000 American Institute of Physics. [S0021-9606(00)01946-2].
引用
收藏
页码:10130 / 10142
页数:13
相关论文
共 28 条
[1]  
[Anonymous], 1994, STRUCTURE DYNAMICS N
[2]   B-PI-3(OU+) X-SIGMA-1(G)+ SYSTEM OF BR2 - ROTATIONAL ANALYSIS, FRANCK-CONDON FACTORS, AND LONG-RANGE POTENTIAL IN B-PI-3(OU+) STATE [J].
BARROW, RF ;
CLARK, TC ;
COXON, JA ;
YEE, KK .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1974, 51 (03) :428-449
[3]   Competition between electronic and vibrational predissociation in Ar-I2(B):: a molecular dynamics with quantum transitions study [J].
Bastida, A ;
Zuñiga, J ;
Requena, A ;
Halberstadt, N ;
Beswick, JA .
CHEMICAL PHYSICS, 1999, 240 (1-2) :229-239
[4]   Vibrational predissociation of the I2•••Ne2 cluster:: A molecular dynamics with quantum transitions study [J].
Bastida, A ;
Zuñiga, J ;
Requena, A ;
Halberstadt, N ;
Beswick, JA .
JOURNAL OF CHEMICAL PHYSICS, 1998, 109 (15) :6320-6328
[5]   Application of trajectory surface hopping to vibrational predissociation [J].
Bastida, A ;
Zuniga, J ;
Requena, A ;
Sola, I ;
Halberstadt, N ;
Beswick, JA .
CHEMICAL PHYSICS LETTERS, 1997, 280 (3-4) :185-188
[6]   Hybrid quantum/classical simulation and kinetic study of the vibrational predissociation of Cl2•••Nen (n=2, 3) [J].
Bastida, A ;
Miguel, B ;
Zuñiga, J ;
Requena, A ;
Halberstadt, N ;
Janda, KC .
JOURNAL OF CHEMICAL PHYSICS, 1999, 111 (10) :4577-4588
[7]  
BESWICK JA, 1981, ADV CHEM PHYS, V47, DOI DOI 10.1002/9780470142677.CH7
[8]   BINDING-ENERGY OF IODINE RARE-GAS VANDERWAALS MOLECULES [J].
BLAZY, JA ;
DEKOVEN, BM ;
RUSSELL, TD ;
LEVY, DH .
JOURNAL OF CHEMICAL PHYSICS, 1980, 72 (04) :2439-2444
[9]   INTERACTION POTENTIALS AND FRAGMENTATION DYNAMICS OF THE NE ... BR2 COMPLEX IN THE GROUND AND ELECTRONICALLY EXCITED-STATES [J].
BUCHACHENKO, AA ;
BAISOGOLOV, AY ;
STEPANOV, NF .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS, 1994, 90 (21) :3229-3236
[10]  
CLINE JI, 1987, STRUCTURE DYNAMICS W, P553