Local density approximation asymptotic corrections

Most of the conventional xc functionals including the local density approximation (LDA) as well as more refined generalized gradient approximations (GGAs) fail to reproduce this asymptotic behavior correctly. As a consequence, these approximations yield rather poor results for properties where the asymptotic region of the xc potential is of crucial importance, e.g. for ionization potentials [4] or excitation energies [5] of atoms and molecules. 

In this section we derive a local density approximation-like expression for the KS exchange energy functional and its derivative such that the latter possesses the correct asymptotic structure both in the classically forbidden and metal-bulk regions. 

Hamel S, Casida ME, Salahub DR (2002b) Exchange-only optimized effective potential for molecules from resolution-of-the-identity techniques Comparison with the local density approximation, with and without asymptotic correction, J Chem Phys, 116 8276-8291... 

Furthermore, they examined the performance of different density functionals, including a local-density approximation and a generalized-gradient approximation as well as the functional of van Leeuwen and Baerends that has been constructed to have the correct asymptotic behaviour. Moreover, they considered different frequency-dependent processes, including third-harmonic generation [THG, corresponding to y( 3electric-field-induced second harmonic generation (EFISH, y( 2electro-optic Kerr effect [EOKO, y(—ft> optical rectification [OR, /S(0 [Pg.161]

Quantum Chemistry in Multiwavelet Bases Time-Dependent Density Functional Theory with Asymptotically Corrected Potentials in Local Density and Generalized Gradient Approximations. 

DPT schemes, which allow to calculate the electron affinities of atoms are based on the exact [59,60] and generalized (local) [61,62] exchange self-interaction-corrected (SIC) density functionals, treating the correlation separately in some approximation. Having better asymptotic behavior than GGA s, like in the improved SIC-LSD methods, one should obtain more... 

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