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Journal of the Korean Chemical Society (JKCS)

ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 29, Number 1
JKCSEZ 29(1)
February 20, 1985 

PMO Theory of Orbital Interaction (Ⅴ). π-π and π*-π* Orbital Interactions

궤도간 상호작용의 PMO 이론 (제5보). π-π 및 π*-π* 궤도간 상호작용
Ikchoon Lee, Kiyull Yang, Nanpyo Lee, Wang Ki Kim

이익춘, 양기열, 이난표, 김왕기
π*-π* 궤도간 상호작용에 관한 섭동식을 유도하였다. 섭동식으로부터 예측되는 π-π와 π*-π* 상호작용간의 중요한 두가지 차이점은 : (ⅰ)에너지분리정도가 π-π 상호작용의 경우보다 π*-π*의 경우가 더 불안정화 되었다. 이러한 예측들은 실험결과들과 MO이론적 계산에 의하여 잘 밝혀졌다. 한편 STO-3G 및 INDO-LCBO 계산방법은 π*-π* 상호작용을 과소평가하고 있음을 알았으며 MO이론적 계산을 이용하여 이러한 π*-π*상호작용을 적절히 표현하는 데는 split valence 기초함수를 사용하여야 함을 밝혔다.

PMO expressions for π*-π* orbital interaction have been derived. Important differences between π-π and π*-π* interactions predicted by PMO expressions are : (ⅰ) energy splitting in π*-π* interaction will be greater than that in π-π interaction, (ⅱ) energy change due to interaction will be more destabilizing in π*-π* than in π-π interaction. These predictions were borne out in experimental data and in results of MO theoretical computations. It was pointed out that both STeO-3G and INDO-LCBO methods underestimate π*-π* orbital interaction and in order to estimate properly with MO theoretical calculation, use of split valence basis set is required.

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