Vertical ionization energies of halogen anions in solution  

作　　者：CHENG XueMin,ZHU Quan,WANG XingJian,LI YunKui & LI XiangYuan College of Chemical Engineering,Sichuan University,Chengdu 610065,China 

出　　处：《Science China Chemistry》2010年第6期1316-1321,共6页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (20873087 and 20903067)

摘　　要：Based on the constrained equilibrium state theory,the nonequilibrium solvation energy is derived in the framework of the continuum model.The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption.The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X(X = Cl,Br,I,Cl2,Br2,I2) in aqueous solution.According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum,our final estimated vertical ionization energies in solution are very close to the experimental observations,while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies.Based on the constrained equilibrium state theory,the nonequilibrium solvation energy is derived in the framework of the continuum model.The formula for spectral shift and vertical ionization energy are deduced for a single sphere cavity with the point charge assumption.The new model is adopted to investigate the vertical ionization for halogen atomic and molecular anions X(X = Cl,Br,I,Cl2,Br2,I2) in aqueous solution.According to the calculation using the CCSD-t/aug-cc-pVQZ method in vacuum,our final estimated vertical ionization energies in solution are very close to the experimental observations,while the traditional nonequilibrium solvation theory overestimates these vertical ionization energies.

关 键 词：VERTICAL IONIZATION energy spectral SHIFT constrained EQUILIBRIUM state 

分 类 号：O611.3[理学—无机化学]