Basis Set Superposition Error on Structures and Complexation Energies of Organo-Alkali Metal Iodides

Bulletin of the Korean chemical society

Sung Hoon Yoon¹  Jongok Won¹  Chang Kon Kim¹  Chan Kyung Kim¹  Hui Zhang¹ 

关键词: Alkali metal iodides;    Basis set superposition error;    Dissociation energy;    Density functional theory;   

DOI  :  

学科分类：化学（综合）

来源: Korean Chemical Society

【 摘 要 】

Theoretical studies have been performed to study the binding characteristics of the alkali metal iodides, M—I (M = Li, Na, K), to poly(ethylene oxide) (PEO, I), poly(ethylene amine) (PEA, II) and poly(ethylene N-methylamine) (PEMA, III) via the B3LYP method. In this study, two types of complexes, singly-coordinated systems (SCS) and doublycoordinated systems (DCS), were considered, and dissociation energies (ツE_D) were calculated both with and without basis set superposition error (BSSE). Two types of counterpoise (CP) approach were investigated in this work, but the ツE_D values corrected by using the function CP (fCP) correction exhibited an unusual trend in some cases due to deformation of the sub-units. This problem was solved by including geometry relaxation in the CP-corrected (GCP) interaction energy. On the other hand, the effects of the BSSE on the structures were very small when the complexes were re-optimized on the CP-corrected (RCP) potential energy surface (PES), even if the bond lengths between X and M⁺ (d_X-M+) and between M⁺ and I- (d_M⁺—I^-) were slightly lengthened. Therefore, neither the GCP nor RCP corrections made much difference to the dissociation energies.

【 授权许可】

Unknown