含能材料
含能材料
함능재료
ENERGETIC MATERIALS
2013年
4期
479-484
,共6页
来蔚鹏%廉鹏%尉涛%陈晓芳%邱少君%常海波
來蔚鵬%廉鵬%尉濤%陳曉芳%邱少君%常海波
래위붕%렴붕%위도%진효방%구소군%상해파
物理化学%溶剂影响%热力学%动力学%理论研究%环加成
物理化學%溶劑影響%熱力學%動力學%理論研究%環加成
물이화학%용제영향%열역학%동역학%이론연구%배가성
physical chemistry%solvent effect%thermodynamics%kinetics%theoretical study%cycloaddition
采用 B3LYP、QCISD、MP2方法在6-311+G*基组水平上对 HN3+NH2CN→5-AT的环加成反应进行了研究,用气相条件下的计算方法结合 SCRF/PCM模型对四氯化碳、丙酮、二甲亚砜、水四种不同溶剂下的反应性能进行计算,探讨了溶剂对反应的影响。结果表明,溶剂的极性对反应的影响不明显,从热力学角度考虑:反应在二甲亚砜溶剂中的平衡常数最大,说明反应在二甲亚砜溶剂中最容易自发进行;从动力学角度考虑:反应在各种溶剂中的速率常数均小于其在气相条件下的速率常数,说明反应在气相条件下更具有动力学优势。300~350 K是该反应的适宜温度。
採用 B3LYP、QCISD、MP2方法在6-311+G*基組水平上對 HN3+NH2CN→5-AT的環加成反應進行瞭研究,用氣相條件下的計算方法結閤 SCRF/PCM模型對四氯化碳、丙酮、二甲亞砜、水四種不同溶劑下的反應性能進行計算,探討瞭溶劑對反應的影響。結果錶明,溶劑的極性對反應的影響不明顯,從熱力學角度攷慮:反應在二甲亞砜溶劑中的平衡常數最大,說明反應在二甲亞砜溶劑中最容易自髮進行;從動力學角度攷慮:反應在各種溶劑中的速率常數均小于其在氣相條件下的速率常數,說明反應在氣相條件下更具有動力學優勢。300~350 K是該反應的適宜溫度。
채용 B3LYP、QCISD、MP2방법재6-311+G*기조수평상대 HN3+NH2CN→5-AT적배가성반응진행료연구,용기상조건하적계산방법결합 SCRF/PCM모형대사록화탄、병동、이갑아풍、수사충불동용제하적반응성능진행계산,탐토료용제대반응적영향。결과표명,용제적겁성대반응적영향불명현,종열역학각도고필:반응재이갑아풍용제중적평형상수최대,설명반응재이갑아풍용제중최용역자발진행;종동역학각도고필:반응재각충용제중적속솔상수균소우기재기상조건하적속솔상수,설명반응재기상조건하경구유동역학우세。300~350 K시해반응적괄의온도。
Cycloaddition reaction HN3 + NH2 CN → 5-AT has been theoretically investigated by B3LYP,QCISD and MP2 methods with 6-311 +G*basis set. The solvent effects on the geometries,reaction path properties,energies,thermodynamic,and kinetic characters in four solvents( carbon tetrachloride,dimethylsulfoxide,aceton,and water)have been studied by using self-consistent reaction field(SCRF)approach with the polarizable continuum model( PCM). Results show that effects of solvent on the geometric characters and reaction path properties are negligible. The equilibri-um constant in dimethylsulfoxide solvent is the largest,so the reaction easier occurred spontaneously in dimethylsulfoxide solvent thermodynamically. The rate constant in the solvents is smaller kinetically than that in gas phase,and 300 to 350 K is the most feasible temperature to the reaction.