卤代甲醛的电离势和电子亲和势的理论研究

利用B3LYP,HF,MP2,MP3和CCSD(T)方法在6-311++G**基组上研究了卤代甲醛在气相中的绝热电离势和绝热电子亲和势。为了描述环境介质的影响,利用MP2/6-311++G**理论研究了卤代甲醛在氯仿、丙酮、硝基甲烷和水中的绝热、垂直电离势和绝热、垂直电子亲和势以及重组能。所有的电离势无论是在气相还是在液相中都是正值,并且液相中的电离势值比气相中的小且随着溶剂介电常数的增大而减小。在MP2/6-311++G**理论上算出的所有的卤代甲醛在气相中的绝热和垂直电子亲和势都是负值,而在液相中却全都变成了正值且随着溶剂介电常数的增大而增大。

Theoretical Study of Ionization Potential and Electron Affinity of Formyhalide

The adiabatic ionization potential and adiabatic electron affinity of formyhalide in the gas phase with B3LYP,HF,MP2,MP3 and CCSD（T） methods at 6-311＋＋G＊＊ basis set were calculated.To describe the effects of the surrounding medium,the adiabatic and vertical ionization potential,adiabatic and vertical electron affinity and reorganization energy of formyhalide in chloroform,acetone,nitromethane and water were performed with MP2/6-311＋＋G＊＊ level.All the ionization potentials were positive values no matter whether in the gas phase or in solutions,and the IPs in solutions were smaller than the results in the gas phase and decreased with the increasing of dielectric constants in solutions.All adiabatic and vertical electron affinities of formylhalide at MP2/6-311＋＋G＊＊ level were negative in the gas phase and all the results changed into positive values in solutions and increased with the increasing of dielectric constants in solutions.