CAJ | 학술논문

用量子化学B3LYP方法在6-311G(d,p)水平上优化了吡咯-HCN氢键复合物,通过振动频率分析确定了两个吡咯-HCN体系稳定构型.为了得到更加精确的氢键作用能,采用相关一致基组aug-cc-pVDZ以及Boys和Bemardi的CP(counterpoise)校正方法消除基组重叠误差后得到C-H…π和N-H…N型复合物的氢键相互作用能.为了确定B3LYP方法计算的相互作用能的可靠性,在MP2/aug-cc-pVDZ水平计算了复合物的氢键相互作用能,结果分别为-25.10和-19.30 kJ·mol-1.采用自然键轨道(NBO)分析考察了吡咯与HCN分子间轨道相互作用.以自洽场理论(SCRF)中的Onsager模型研究了不同极性溶剂对吡咯-氰化氢体系N-H…N型氢键几何构型,频率位移,电荷分布以及相对能量的影响.研究发现,当溶液的介电常数在1.5～30.0范围时,溶液作用十分显著,而当介电常数超过30.0以后,溶液作用已经达到了极限.
용양자화학B3LYP방법재6-311G(d,p)수평상우화료필각-HCN경건복합물,통과진동빈솔분석학정료량개필각-HCN체계은정구형.위료득도경가정학적경건작용능,채용상관일치기조aug-cc-pVDZ이급Boys화Bemardi적CP(counterpoise)교정방법소제기조중첩오차후득도C-H…π화N-H…N형복합물적경건상호작용능.위료학정B3LYP방법계산적상호작용능적가고성,재MP2/aug-cc-pVDZ수평계산료복합물적경건상호작용능,결과분별위-25.10화-19.30 kJ·mol-1.채용자연건궤도(NBO)분석고찰료필각여HCN분자간궤도상호작용.이자흡장이론(SCRF)중적Onsager모형연구료불동겁성용제대필각-청화경체계N-H…N형경건궤하구형,빈솔위이,전하분포이급상대능량적영향.연구발현,당용액적개전상수재1.5～30.0범위시,용액작용십분현저,이당개전상수초과30.0이후,용액작용이경체도료겁한.
The hydrogen bonds between the HCN and pyrrole were subjected to density functional theory (DFT) calculations using 6-311G( d, p) basis set. The structures and vibrational frequencies of the hydrogen-bonding complexes were computed at the B3LYP/6-311G( d, p) level. To obtain the accurate binding energies, single-point calculations were performed at the B3LYP/aug-cc-pVDZ and MP2/aug-cc-pVDZ level, respectively. After BSSE (basic set superthe H - N vibration mode. The solvent effect is obvious when dielectric constant s is within 1.5 ～ 30. 0 and is weak when ε exceeds 30.0.