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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 42, Number 1
JKCSEZ 42(1)
February 20, 1998 

 
Title
Quantum Mechanical Investigation for the Structure and Vibrational Frequencies of Dimethyldioxirane

Dimethyldioxirane의 분자구조와 Vibrational Frequencies에 대한 양자역학적 고찰
Author
Chang-Duk Kang, Seung-Joon Kim*

강창덕, 김승준
Keywords
Abstract
Dimethyldioxirane[(CH3)2CO2]의 분자구조, vibrational friquencies 그리고 infrared(IR) 스펙트럼의 세기등에 대한 이론적 연구를 high level ab initio 양자역학적 방법(CISD,CCSD, CCDS(T))을 사용하여 수행하였다. 분자구조의 경우 C-O와O-O에 대한 결합길이는 prent dixorane(CH2O2)과 유사한 결과를 보여주었으며, electrone corrlation effect의 영향이 C-C나 C-H결합길이 보다 더 크게 작용하였다. 사용된 basis sets(DZ,DZP, TZP, 그리고 TZ2P)에 대해서는 polarization function의 역할이 매우 중요한 것으로 나타났으며 triple zeta(TZ)에 의한 효과는 상대적으로 나타났다. 한편 계산된 harmonic vibrational frequency들을 실험결과 및 다른 이론 계산결과와 비교, 분석하였으며 IR intencity에 근거하여 각 vibrational mode를 assion하였다.

The geometrical parameters, vibrational frequencies, and IR intensities for primary ozonide (POZ), secondary ozonide (SOZ) and carbonyl oxide as the intermediates of alkene-ozone reaction have been predicted using high level ab initio quantum mechanical method with various basis sets. In general, the polarization function decreases bond lengths and bond angles, while the electron correlation effect increases bond lengths slightly. The electronic structure of carbonyl oxide has been predicted to be zwitterionic structure and energy difference between zwitterionic and diradical structure is evaluated to be 22.4 kcal/mol at TZ2P CISD level of theory. The experimental vibrational frequencies and IR intensities of POZ and SOZ will be compared and discussed with our high level theoretical predictions.

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