화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.116, No.22, 5497-5500, 2012
Negative Electron Affinities from DFT: Influence of Asymptotic Exchange-Correlation Potential and Effective Homogeneity under Density Scaling
The influence of the asymptotic exchange-correlation potential and density-scaling homogeneity on negative electron affinities determined using the approach of Tozer and De Proft [J. Phys. Chem. A 2005, 109, 8923] is investigated. Application of an asymptotic correction to the potential improves the accuracy for several of the systems with the most negative affinities, reflecting their diffuse lowest unoccupied orbitals. For systems with modest affinities, it reduces the accuracy marginally. Enforcing a near-exact effective homogeneity through a simple shift in the potential leads to improved correlation with experimental values but significantly overestimated affinities. Optimal effective homogeneities are therefore determined, and a simple scheme is proposed for enforcing an average optimal value. Application of the scheme to a series of organic molecules maintains the excellent correlation with the experimental values while significantly reducing the absolute errors.