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Intramolecular dynamics of cationic van der Waals complexes: Case study of ArHCl +
Author(s) -
Zülicke L.,
Neumann R.,
Zuhrt Ch.,
Schretter J.
Publication year - 2000
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/1097-461x(2000)80:3<486::aid-qua19>3.0.co;2-y
Subject(s) - intramolecular force , chemistry , van der waals force , excited state , diatomic molecule , multireference configuration interaction , excitation , atomic physics , ground state , electronic structure , molecule , computational chemistry , configuration interaction , physics , quantum mechanics , stereochemistry , organic chemistry
The structure and internal dynamics of cationic van der Waals complexes Rg n M + , where Rg denotes a rare‐gas atom and M a diatomic molecule, turn out to be remarkably complicated, and information on such systems is still rather scarce. The present study reports on results of a case study of ArHCl + , starting with extensive multireference configuration interaction calculations of the potential energy surfaces (PES) for several low‐lying electronic states. The two lowest A ′ doublet‐state PES are analytically fitted and their topography is analyzed. For the electronic ground‐state PES, 1 2 A ′, the full set of vibrational states is calculated, and the time‐dependent intramolecular dynamics is investigated quantum mechanically (wavepackets) as well as classically (trajectories), particularly with respect to symptoms of irregularity. One result is that the geometrical structure of the complex in its electronic ground state can be controlled by different vibrational excitation. The peculiarities of the excited‐state 2 2 A ′ PES are used to discuss possible photoprocesses and their control by appropriately chosen infrared (IR) and ultraviolet (UV) laser pulses leading to different fragmentation channels, ArH + ( X 1 Σ + )+Cl( 2 P o ) or Ar + ( 2 P o )+HCl( X 1 Σ + ). © 2000 John Wiley & Sons, Inc. Int J Quant Chem 80: 486–498, 2000