CAJ | 학술논문

在密度泛函理论(DFT)B3LYP/6-311+G*水平上计算研究了叠氮二氟硼多聚体(F2BN3)n (n=1～4),获得了它们的结构和热力学性质,讨论了几何参数随聚合度的变化趋势.多聚体(F2BN3)2-4的优化构型均为由不同子体系的叠氮基α-N和B原子相连形成的环状结构.三聚体的船扭式构象比椅式构象的结合能低10.54 kJ*mol-1;四个新获得的四聚体的结合能差异较大,大小为3.1～45.65 kJ*mol-1.由焓变可知,单体形成二聚体在热力学上是不利的,而形成三聚体和四聚体在高达1200 K的温度下是有利的,同时分析比较了后续反应的热力学参数.
재밀도범함이론(DFT)B3LYP/6-311+G*수평상계산연구료첩담이불붕다취체(F2BN3)n (n=1～4),획득료타문적결구화열역학성질,토론료궤하삼수수취합도적변화추세.다취체(F2BN3)2-4적우화구형균위유불동자체계적첩담기α-N화B원자상련형성적배상결구.삼취체적선뉴식구상비의식구상적결합능저10.54 kJ*mol-1;사개신획득적사취체적결합능차이교대,대소위3.1～45.65 kJ*mol-1.유함변가지,단체형성이취체재열역학상시불리적,이형성삼취체화사취체재고체1200 K적온도하시유리적,동시분석비교료후속반응적열역학삼수.
Density functional theory (DFT) was employed to study on (F2BN3)n (n=1～4) clusters at the B3LYP/6-311+G* level. A set of the structural and thermodynamic properties have been obtained. Trends in structural parameters with oligomerization degree n are discussed. The optimized clusters (F2BN3)2-4 all possess cyclic structure formed by B atoms bridged by the α-nitrogen of the azide groups. The boat-twisting conformation lies 10.54 kJ*mol-1 lower in binding energies than the chair isomer for the trimers. The four tetramers newly gained show greatly binding energy differences in range of 3.1～45.65 kJ*mol-1. The dimerization is thermodynamically unfavorable by the enthalpy. However, the formations of trimers and tetramers are very favorable thermodynamically even at high (1200 K) temperatures. Comparisons of the thermodynamic parameters of subsequent oligomerization are also given.