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Investigation into the metallophilic interaction in coinage-metal halides: an ab initio study of CMX (CM = Cu and Ag, X = F − I)

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Abstract

Investigation of the metallophilic interactions of the title coinage-metal halide series, CMX (CM = Ag and Cu, X = F − I), and their cationic and anionic systems, were performed at CCSD(T) theoretical level with extended basis sets. Natural bond orbital analysis shows that the interactions come mainly from the overlap of the sp hybrid on the halogen and the spd hybrid on the coinage-metal atom. Electron density deformation analysis demonstrates a pronounced electron accumulation in the interaction region between the heavier X and the coinage-metal atoms, and suggests a covalent character of the interaction. Positive Laplacian values and negative total energy densities at bond critical points (BCPs) show the “intermediate” character of the interactions. Reduced density gradient analysis visualizes the interaction; a linear relationship between energy densities and eigenvalues can be found at BCPs.

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Acknowledgments

The authors would like to acknowledge Professor M. Dolg for helpful discussions. The research was supported by the Natural Science Foundation of China (Grant No. U1404210) and Program for Innovative Research Team (in Science and Technology) in University of Henan Province (No. 13IRTSTHN017).

Conflict of interest

The authors declare that they have no conflict of interest. This article does not contain any studies with human participants or animals performed by any of the authors. Informed consent was obtained from all individual participants included in the study.

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Authors and Affiliations

  1. Institute for Computational Materials Science, School of Physics and Electronics, Henan University, Kaifeng, 475004, People’s Republic of China

    Xinying Li

  2. College of Physics and Electronic Engineering, Henan Normal University, Xinxiang, 453007, People’s Republic of China

    Zhen-duo Geng

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  1. Xinying Li
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  2. Zhen-duo Geng
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Correspondence to Xinying Li.

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Li, X., Geng, Zd. Investigation into the metallophilic interaction in coinage-metal halides: an ab initio study of CMX (CM = Cu and Ag, X = F − I). J Mol Model 21, 205 (2015). https://doi.org/10.1007/s00894-015-2745-7

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  • DOI: https://doi.org/10.1007/s00894-015-2745-7

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