Pseudorotation-driven dynamical structure of the tropyl radical
SCIE
SCOPUS
- Title
- Pseudorotation-driven dynamical structure of the tropyl radical
- Authors
- Yi, HB; Lee, HM; Suh, SB; Shin, SK; Kim, KS
- Date Issued
- 2006-10-28
- Publisher
- AMER INST PHYSICS
- Abstract
- Despite intensive studies of the neutral tropyl radical, none of its structure, energetics, and vibrational modes are still clear. This system has puzzled scientists for over a decade since one vibrational mode frequency sharply varies from imaginary number 3000i cm(-1) to the real number 6000 cm(-1), depending on the calculation methods employed. We find that the origin of this peculiar mode is due to the pseudorotation (omega(irot)) involved in the interconversion of two nearly isoenergetic Jahn-Teller configurations (elongated structure B-2(1) and compressed structure (2)A(2) with C-2v symmetry). Here, we first report that this interconversion is not via D-7h or C-2v symmetry configuration but via C-s symmetry (i.e., by changing the C-2v axis). This interconversion barrier is found negligibly small. Thus, the two conformers are considered to be not two different structures but a dynamically identical structure with partial quantum statistical distributions on the potential energy surface. Owing to the nearly barrierless pseudorotation, the overall structure in a short time scale (less than femtosecond) would be C-s-like between (2)A(2) and B-2(1) configurations with small fluctuation of bond distances. However, the dynamical transitions between the B-2(1) and (2)A(2) configurations via 14 different pseudorotation pathways would make the tropyl radical have the effective D-7h structure in either a nonshort time scale (greater than femtosecond) or at nonlow temperatures, which explains the high temperature electron spin resonance experiments. (c) 2006 American Institute of Physics.
- URI
- https://oasis.postech.ac.kr/handle/2014.oak/23738
- DOI
- 10.1063/1.2358355
- ISSN
- 0021-9606
- Article Type
- Article
- Citation
- JOURNAL OF CHEMICAL PHYSICS, vol. 125, no. 16, 2006-10-28
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