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A Theoretical Study of the Formation of Benzene Excimer: Effects of Geometry Relaxation and Spin-state Dependence
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  • A Theoretical Study of the Formation of Benzene Excimer: Effects of Geometry Relaxation and Spin-state Dependence
  • A Theoretical Study of the Formation of Benzene Excimer: Effects of Geometry Relaxation and Spin-state Dependence
저자명
Kim. Dongwook
간행물명
Bulletin of the Korean Chemical Society
권/호정보
2014년|35권 9호|pp.2738-2742 (5 pages)
발행정보
대한화학회
파일정보
정기간행물|ENG|
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이 논문은 한국과학기술정보연구원과 논문 연계를 통해 무료로 제공되는 원문입니다.
서지반출

기타언어초록

Geometry relaxation effects on the formation of benzene excimer were investigated by means of ab initio calculation at SOS-CIS($D_0$)/aug-cc-pVDZ level. In the case of T-shaped dimer configuration, intermolecular interactions in the excited states are found to be nearly the same as those in the ground state and structural deformations are limited within a single molecule; the geometry relaxation effects are then negligible and singlet-triplet energy gap remains constant. As for face-to-face eclipsed dimer, on the other hand, both molecules undergo structural change. As a result, intermolecular interactions in the excited states are significantly different than those in the ground state. Although the intermolecular distances obtained from potential energy curve calculation with frozen molecular structures are in qualitative agreement, the excited-state binding energies are notably overestimated with respect to those at optimized structures. In particular, the effects are calculated to be larger in $T_1$ state and hence singlet-triplet energy gap, which reduces markedly in this configuration, is underestimated without relaxation.