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Theoretical Studies on the Interaction of the CO…CO+ Coupling System Using Density Functional Theory
Li Ping,Bu Yuxiang
Author NameAffiliationE-mail
Li Ping Institute of Theoretical Chemistry, Shandong University, Jinan 250100  
Bu Yuxiang Institute of Theoretical Chemistry, Shandong University, Jinan 250100; Department of Chemistry, Qufu Normal University, Qufu 273165 byx@sdu.edu.cn  
Abstract:
Three hybrid density functional theory (DFT) methods (B3LYP (Becke′s three-parameter Hybrid Functional using the Lee-Yang-Parr Correlation Function), B3P86 and B3PW91 (Becke′s three-parameter Hybrid Functional with Perdew86 and perdew/Wang91 Correlation Functions respectively)) and two appropriate basis sets (6-311+G* and aug-cc-PVDZ) have been employed to investigate all the possible structures of the CO…CO+ coupling system on the global potential energy surface. The results show that there are three relative stable complexes verified by none imaginary frequencies. Among them complexes A and B are co-plane structures except complex C and the subtle difference between complexes B and C is the dihedral of them. Complex A is the most stable structure through the comparison of the energies of three complexes. The orbital binding character using the population analysis and covalent bond orders between atoms within the AIM methodology is also calculated at B3LYP/6-311+G* level. Then the precise interaction energies of the three complexes have been obtained through the corrections of the basis set superposition error (BSSE) and the zero point vibration energy (ZPVE), and the full counterpoise procedure (FCP) recommended by Boys and Bernardi has been applied for the BSSE correction. The results of the interactive energies are 252.47, 126.70, 127.12 kJ/mol for complexes A, B and C respectively, which are in agreement with the literature data reported before. Finally, we list the normal vibrational frequencies and corresponding IR intensity of the three complexes at B3LYP/6-311+G* level. Moreover, the analytical figure of normal vibration frequencies for complex A is also displayed at the same time. All computations indicate that the interaction between CO and CO+ is strong and DFT methods can serve as an effective tool to predict the molecular geometry, thermodynamics and frequencies that are well close to the experimental values.
Key words:  CO…CO+ coupling system, Density Functional Theory, Interaction energy, Orbital binding analysis
FundProject:国家自然科学基金(29973022)、高等院校国家重点实验室访问学者基金及高等学校骨干教师培养基金资助课题.
CO…CO+ 体系相互作用的密度泛函理论研究
李平,步宇翔*
摘要:
在三种密度泛函方法(B3LYP、B3P86及B3PW91)和两种适宜基组(6-311+G*及aug-cc-PVDZ)水平上,对CO…CO+耦合体系可能存在的相互作用复合物进行了全自由度能量梯度优化,发现势能面上存在三个能量极小点,进而作了振动频率分析加以确认.其中结构A、 B为共平面型结构, C为非共面型结构. 比较了它们之间的相对稳定性,并对其进行了轨道成键分析,计算了各原子之间的键级,同时探讨了最稳定结构A的正则振动模式. 通过消除基函数引起的基组叠加误差(BSSE)和零点振动能(ZPVE)的校正,精确求算出复合物结构A、 B和C的相互作用能△E分别为252.47、 126.70和127.12 kJ/mol, 表明CO和CO+之间存在较强的相互作用.
关键词:  CO…CO+耦合体系  密度泛函理论  相互作用能  轨道成键分析
DOI:10.1088/1674-0068/15/6/412-418
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