Chemistry of vibronic coupling, part 4: Off-diagonal vibronic coupling constants across the periodic table

Polish Journal of Chemistry

Volumn 75, Issue 11, 2001, Pages 1603-1659

  Grochala, W ^a   Hoffmann, R ^a  

^a Department of Obstetrics Gynecology   (United States)

Author keywords

Avoided crossing; Hardness; Quantum mechanical calculations; Triatomic radicals; Vibronic coupling

Indexed keywords

EID: 0035648733     PISSN: 01375083     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (110)

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62. Dissociation of symmetric linear triatomic proceeds along a combination of antisymmetric and symmetric stretching coordinates. In this paper we study the potential energy surface of a triatomic along an antisymmetric stretching coordinate, with symmetric stretching coordinate optimized and then frozen.
63. 2. The presence of an unpaired electron in the species studied here usually results in strong vibronic coupling in these systems, in contrast to the closed-shell ones.
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65. g for all triatomics investigated in this paper also correlates very well with f.
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108. From both computations and theoretical models we know how to reach the goal of large vibronic coupling. However, there is a limit to the extent and significance of large vibronic coupling. This limit is determined by the thermodynamic stability of a molecule toward asymmetric dissociation. If the coupling is so large that it leads to an ABA molecule's dissociation (such dissociation proceeds along a combination of antisymmetric and symmetric stretching coordinates), then that coupling in a way has no real physical importance. A linear symmetric structure (the point at which G is determined) is then too far away from any real equilibrium geometry. Hence, "prodissociative", enormously large coupling constants might not be useful in pointing to molecules which may have interesting properties.
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110. We have made some progress toward a physical justification of the use of f; this work will be published elsewhere.