CAJ | 학술논문

用密度泛函方法，计算研究1，5-二氨基四唑（DAT）的电子结构及异构化反应机理。在B3LYP/6-311G水平下，对涉及反应各驻点的几何结构、振动频率、自然键轨道、以及零点能（ ZPE）进行了计算；用内禀反应坐标理论（ IRC）获得反应的最小能量路径（MEP），在耦合簇理论的CCSD（T）方法下计算单点能得到了反应的最小势能曲线；并且用传统过渡态理论（TST）、Eckart 隧道校正理论（TST/Eckart）和变分过渡态理论（CVT），计算了200～1000 K的反应速率常数。计算结果表明，DAT分子中的N（4）和N（9）易参与金属原子配位，形成一系列以DAT为配体的配位化合物。异构化合成DAT反应为叠氮基关环机理，气态情况下该反应为放热且自发反应，反应活化能较低。
용밀도범함방법，계산연구1，5-이안기사서（DAT）적전자결구급이구화반응궤리。재B3LYP/6-311G수평하，대섭급반응각주점적궤하결구、진동빈솔、자연건궤도、이급영점능（ ZPE）진행료계산；용내품반응좌표이론（ IRC）획득반응적최소능량로경（MEP），재우합족이론적CCSD（T）방법하계산단점능득도료반응적최소세능곡선；병차용전통과도태이론（TST）、Eckart 수도교정이론（TST/Eckart）화변분과도태이론（CVT），계산료200～1000 K적반응속솔상수。계산결과표명，DAT분자중적N（4）화N（9）역삼여금속원자배위，형성일계렬이DAT위배체적배위화합물。이구화합성DAT반응위첩담기관배궤리，기태정황하해반응위방열차자발반응，반응활화능교저。
The electronic properties of 1, 5-diamino-tetrazole( DAT) and isomerization reaction kinetics were studied based on densi-ty functional theory.The geometry structure, vibration frequencies, natural bonding orbital, and zero point energy ( ZPE) of station-ary points involved in the reaction was calculated at B3LYP/6-311G level of theory.The intrinsic reaction coordinate theory (IRC) was used to obtain the minimum energy path (MEP).The reaction potential energy curve was obtained by calculating the single point energy with CCSD ( T) method.The rate constants are evaluated from 200 to 1000 K using transition state theory ( TST) , TST/Eckart and Canonical variational transition state theory (CVT).Results show that N(4) and N(9) in DAT molecule participate easily in coordination with metal atoms, forming a series of coordination compounds.The isomerization reaction for DAT displays azide-cyclization mechanism.At gaseous case, the reaction is exothermic and spontaneous, with lower reaction activation energy.