羰基氧化物RR^1COO的电子结构

本文采用6-31G基组的abinitio方法对羰基氧化物RR^1COO(R,R^1=H,F,CH~3)进行几何构型优化计算,研究其基态的电子结构。结果表明,RR^1COO的稳定结构为双自由基型,其单重态和双重态的相对稳定性受取代基的影响。H~2COO、H(CH~3)COO和(CH~3)~2COO的基态为单重态(^1A),HFCOO和F~2COO的基态为三重态(^3A),HFCOO和H(CH~3)COO的顺式结构比反式稳定。

The electronic structures of carbonyl oxides

In this paper, ab initio calculations are performed on carbonyl oxides RR^1COO (R, R^1=H, F, CH~3) using 6-31G basis set in order to study the electronic structures of the ground states. All geometries are optimized with the energy gradient technique. The calculated results predict that the stable structure is a diradical, the relative energies between singlets and triplets are influenced by the substituents. And the ground states for H~2COO, H(CH~3)COO, and (CH~3)~2COO are singlet (^1A), the ground states for HFCOO, and F~2COO are triplet (^3A). The cis forms of HFCOO and H(CH~3)COO are found to be more stable than the corresponding transforms.