N_2H_4-CH_3OH氢键团簇体系的从头计算  

Ab Initio Calculation on Hydrogen\|bonded Cluster: N_2H_4-CH_3OH

作　　者：胡勇军[1] 吕日昌[1] 蔡永[1] 王秀岩[1] 

机构地区：[1]中国科学院大连化学物理研究所分子反应动力学国家重点实验室,大连116023

出　　处：《Chinese Journal of Structural Chemistry》2001年第1期69-75,共7页结构化学（英文）

基　　金：国家自然科学基金资助项目

摘　　要：用从头计算法研究了 (N2 H4-CH3OH)氢键团簇体系。分别在HF/6 31G 和HF/6 31G 水平上对它们的中性和离子团簇进行几何全优化 ,得到了 3种中性混合团簇稳定构型和离子混合团簇稳定构型 ,并对其能量和稳定性进行了比较。讨论了 3种不同构型离子团簇可能的解离通道。给出了质子化混合团簇的稳定构型 ,并对其可能的解离通道进行了讨论。文中最后计算出N2 H4,CH3OH ,(N2 H4-CH3OH)团簇的质子亲和能 (PA) ,分别为 :2 0 6.7kcal/mol,1 78.3kcal/mol,2 2 7.5kcal/mol,其中质子亲和能PAcalc[N2 H4]与实验值PAexp[N2 H4]=2 0 4 .8kcal/mol符合得很好。Ab initio calculations on the hydrogen bond clusters N2H4 - CH3OH have been carried out. Three stable structures of neutral and ionic clusters were obtained. Their energies and stabilities were compared and their dissociated channels were discussed. The stable structure of protonated mixed cluster (N2H4 - H-CH3OH)(+) was calculated and its dissociated channel was discussed. The proton affinity (PA) of the hydrazine molecule, the methonal molecule and their mixed duster (N2H4 - CH3OH) were obtained, which were PA[N2H4] = 206.7 kcal/mol, PA[CH3OH] = 178.3 kcal/mol, PA[N2H4 - CH,OH] = 227.5 kcal/mol, respectively. The calculated value of the proton affinity of the hydrazine molecule was in good agreement with the experimental value which is PA(exp)[N2H4] = 204.8 kcal/mol.

关 键 词：肼 甲醇 团簇 从头计算 氢键 解离通道 构型 

分 类 号：O641[理学—物理化学]