The weak covalent bond in NgAuF (Ng=Ar, Kr, Xe): A challenge for subsystem density functional theory

被引:35
作者
Beyhan, S. Maya [1 ]
Gotz, Andreas W. [1 ]
Jacob, Christoph R. [2 ]
Visscher, Lucas [1 ]
机构
[1] Vrije Univ Amsterdam, Amsterdam Ctr Multiscale Modeling, NL-1081 HV Amsterdam, Netherlands
[2] ETH, Phys Chem Lab, CH-8093 Zurich, Switzerland
关键词
argon compounds; bonds (chemical); density functional theory; electric moments; krypton compounds; molecular moments; xenon compounds; CONSTRAINED ELECTRON-DENSITY; KINETIC-ENERGY FUNCTIONALS; KOHN-SHAM EQUATIONS; GENERALIZED GRADIENT APPROXIMATION; THOMAS-FERMI THEORY; SOLVATION FREE-ENERGIES; MOLECULAR-PROPERTIES; MICROWAVE-SPECTRA; EXCHANGE; SYSTEMS;
D O I
10.1063/1.3297886
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We have assessed the accuracy of a representative set of currently available approximate kinetic-energy functionals used within the frozen-density embedding scheme for the NgAuF (Ng=Ar, Kr, Xe) molecules, which we partitioned into a Ng and a AuF subsystem. Although it is weak, there is a covalent interaction between these subsystems which represents a challenge for this subsystem density functional theory approach. We analyzed the effective-embedding potentials and resulting electron density distributions and provide a quantitative analysis of the latter from dipole moment differences and root-mean-square errors in the density with respect to the supermolecular Kohn-Sham density functional theory reference calculation. Our results lead to the conclusion that none of the tested approximate kinetic-energy functionals performs well enough to describe the bond between the noble gas and gold adequately. This observation contributes to the growing evidence that the current procedure to obtain approximate kinetic-energy functionals by reparametrizing functionals obtained via the "conjointness" hypothesis of Lee, Lee, and Parr [Phys. Rev. A 44, 768 (1991)] is insufficient to treat metal-ligand interactions with covalent character.
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页数:9
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