Comparative performance of exchange and correlation density functionals in determining intermolecular interaction potentials of the methane dimer.
We have calculated the interaction potentials of the methane dimer for the minimum-energy D(3d) conformation using the density functional theory (DFT) with 90 density functionals chosen from the combinations of nine exchange and 10 correlation functionals. Several hybrid functionals are also considered. While the performance of an exchange functional is related to the large reduced density gradient of the exchange enhancement factor, the correlation energy is determined by the low-density behavior of a correlation enhancement factor. Our calculations demonstrate that the correlation counterpart plays an equally important role as the exchange functional in determining the van der Waals interactions of the methane dimer. These observations can be utilized to better understand the seemingly unsystematic DFT interaction potentials for weakly bound systems.
Chao
Sheng D
SD
Institute of Applied Mechanics, National Taiwan University, Taipei 106, Taiwan ROC. sdchao@spring.iam.ntu.edu.tw
Li
Arvin Huang-Te
AH