CAJ | 학술논문

应用量子化学的不同方法和基组计算了 Hg 与 HF 反应体系中有关分子结构的几何参数和反应焓变，并与美国国家标准技术局(NIST)中的热力学参数比较验证.结果表明，综合考虑时间及精度，以MP2/Stevens基组的组合为最佳.以此为基础进行优化，得出 Hg 与 F 反应各体系的几何构型，获得反应的微观方程.采用经典过渡态理论计算了298~1500 K 和0．001~3 MPa范围内各反应的动力学参数.计算结果表明：相比 HF 对 Hg0反应的影响， HF更易与 HgF反应；Hg与F 反应体系的反应速率均随温度、压力的升高而上升，相比温度，压力对反应速率的影响不明显.
응용양자화학적불동방법화기조계산료 Hg 여 HF 반응체계중유관분자결구적궤하삼수화반응함변，병여미국국가표준기술국(NIST)중적열역학삼수비교험증.결과표명，종합고필시간급정도，이MP2/Stevens기조적조합위최가.이차위기출진행우화，득출 Hg 여 F 반응각체계적궤하구형，획득반응적미관방정.채용경전과도태이론계산료298~1500 K 화0．001~3 MPa범위내각반응적동역학삼수.계산결과표명：상비 HF 대 Hg0반응적영향， HF경역여 HgF반응；Hg여F 반응체계적반응속솔균수온도、압력적승고이상승，상비온도，압력대반응속솔적영향불명현.
The geometrical parameters of molecules reacted in Hg/HF reaction system as well as the reac-tion's enthalpy changes were calculated using different quantum chemistry methods and basis sets.In addi-tion,the calculating results were compared with that from literatures and NIST experimental data.The comparison showes that,in view of time and accuracy,the MP2/Stevens was the optimal combination,by that we could obtain reaction equations and their molecules structures.Further more,the reaction kinetic parameters under the conditions of 298 K to1 500 K and 0.001 MPa to 3 MPa were calculated by employing transition state theory.The calculation indicates that the HF is inclined to react with HgF rather than Hg0 .The reaction rate raises as the temperature and the pressure increases,of which the temperature af-fects much than the pressure.