Vibrational predissociation and intramolecular vibrational energy redistribution three-dimensional quantum dynamics of ArI[sub 2]

Journal Article · Thu Mar 02 00:00:00 EST 1995 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100009a008· OSTI ID:6492356

Gray, S K ^[1]; Roncero, O ^[2]

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1. Argonne National Lab., IL (United States)
2. Inst. Matematicas y Fisica Fundamental, Madrid (Spain)

A detailed theoretical study of an empirical potential model for ArI[sub 2]([nu][prime]) [yields] Ar + I[sub 2]([nu]<[nu][prime]), with zero total angular momentum, is presented. With a reasonable choice of parameters for the potential, three-dimensional quantum dynamics calculations yield a nonmonotonic variation in the main resonance decay constant with initial I[sub 2] vibrational excitation [nu][prime]. This behavior is attributed to a few-state intramolecular vibrational energy redistribution (IVR) mechanism. The main resonances contain large contributions from zero-order bright' states with [nu][prime] quanta in I[sub 2] and zero-point energy in the van der Waals modes. They also contain varying degrees of dark' states associated with [nu][prime] - 1 and [nu][prime] - 2 quanta in I[sub 2] and stretch/bend excitations in the van der Waals modes. The varying degree of interaction between bright and dark states leads to the strong variation in main resonance decay constants. We also investigate the quantum dynamics of certain excited vdW stretch/bend states, which show related behavior. Recent experimental work, however, suggests that no unusual IVR effects occur in ArI[sub 2]. Possible reasons for this apparent discrepancy between theory and experiment are suggested. 42 refs., 6 figs., 3 tabs.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 6492356
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 99:9; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
99 GENERAL AND MISCELLANEOUS//MATHEMATICS, COMPUTING, AND INFORMATION SCIENCE
ARGON IODIDES
PREDISSOCIATION
QUANTUM ELECTRODYNAMICS
MATHEMATICAL MODELS
PHYSICAL CHEMISTRY
THEORETICAL DATA
VIBRATIONAL STATES
ARGON COMPOUNDS
CHEMISTRY
DATA
DISSOCIATION
ELECTRODYNAMICS
ENERGY LEVELS
EXCITED STATES
FIELD THEORIES
HALIDES
HALOGEN COMPOUNDS
INFORMATION
IODIDES
IODINE COMPOUNDS
NUMERICAL DATA
QUANTUM FIELD THEORY
RARE GAS COMPOUNDS
400201* - Chemical &amp; Physicochemical Properties
661100 - Classical &amp; Quantum Mechanics- (1992-)
990200 - Mathematics &amp; Computers