Quantum dynamical calculations for the vibrational predissociation of the He–ICl complex: Product rotational distribution

Three‐dimensional quantum close‐coupling calculations are presented for the vibrational predissociation of He–ICl B state complexes containing two quanta of ICl vibrational excitation. The dynamics are evaluated for the lowest quasibound van der Waals levels of He–ICl with total angular momentum J=0 and 1. The vibrational predissociation lifetime and final ICl B(v=1, j ) rotational distribution are calculated using the golden rule approximation. The calculated ICl product rotational distributions are broadly bimodal with maxima at j=7 and 15, as experimentally observed. The computed rotational distributions exhibit pronounced oscillations, which are expected to be suppressed when averaged over the initial angular momentum distribution sampled in the experiment. The theoretical analysis points to the dominant role of final‐state interactions in determining the rotational distribution of the ICl fragments. The zero‐point bending motion of the He–ICl complex and the coupling between the initial and final vib...

[1]  K. Janda,et al.  Product state distributions for the vibrational predissociation of NeCl2 , 1989 .

[2]  O. Roncero,et al.  Decay of vibrationally excited states of the Ne…Cl2 complex , 1989 .

[3]  M. Lester,et al.  Rotational rainbows in the vibrational predissociation of ICl–He complexes , 1988 .

[4]  M. Lester,et al.  Evidence for final state interactions in the vibrational predissociation of ICl–Ne complexes , 1988 .

[5]  K. Janda,et al.  State‐to‐state vibrational predissociation dynamics and spectroscopy of HeCl2: Experiment and theory , 1988 .

[6]  K. Janda,et al.  Vibrational and rotational wave functions for the triatomic van der Waals molecules helium dichloride, neon dichloride, and argon dichloride , 1988 .

[7]  M. Lester,et al.  Near threshold photofragmentation dynamics of ICl–Ne A state van der Waals complexes , 1988 .

[8]  K. Janda,et al.  Three‐dimensional quantum mechanical study of Ne⋅⋅⋅Cl2 vibrational predissociation , 1987 .

[9]  R. Schinke.  The rotational reflection principle in the direct photodissociation of triatomic molecules. Close‐coupling and classical calculations , 1986 .

[10]  M. Lester,et al.  Dynamical effects in the vibrational predissociation of ICl–rare gas complexes , 1986 .

[11]  M. Lester,et al.  Direct lifetime and nascent product distribution for the vibrational predissociation of ICl–Ne A(3Π1) state van der Waals complexes , 1986 .

[12]  M. Lester,et al.  Photophysics of He-ICl van der Waals complexes: Excitation to predissociative levels in the B state , 1985 .

[13]  G. Delgado-barrio,et al.  Three‐dimensional vibrational predissociation of the van der Waals complex He⋅⋅⋅I2(B). A quasiclassical study , 1983 .

[14]  I. McDermid,et al.  B 3 Π(0+) states of IF, ICI and IBr. Part 1 —Calculation of the RKR turning points and Franck–Condon factors for the B–X Systems , 1976 .

[15]  A. L. G. Rees,et al.  The calculation of potential-energy curves from band-spectroscopic data , 1947 .