Assessment of exchange-correlation functionals for the calculation of dynamical properties of small clusters in time-dependent density functional theory

被引:107
作者
Marques, MAL [1 ]
Castro, A
Rubio, A
机构
[1] Univ Valladolid, Dept Fis Teor, E-47011 Valladolid, Spain
[2] Univ Coimbra, Dept Fis, Ctr Fis Computac, P-3004516 Coimbra, Portugal
[3] Ecole Polytech, CNRS, CEA, Lab Solides Irradies, F-91128 Palaiseau, France
[4] Donostia Int, Phys Ctr, San Sebastian 20018, Spain
关键词
D O I
10.1063/1.1385368
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 present a detailed study of different exchange-correlation (xc) functionals in describing the dynamical properties of finite systems. For that purpose, we calculated the static polarizabilities, ionization potentials, and optical absorption spectrum of four small clusters, Na-2, Na-4, SiH4, and Si2H6, using a real-space, real-time technique. The computed static polarizabilities and ionization potentials seem to be in rather good agreement with the available experimental data, once the proper asymptotics of the potential are taken into account. The same conclusion holds for the absorption spectra, although the xc kernels in use do not provide a sufficiently strong attractive interaction between electrons and holes, leading to spectra slightly shifted towards higher energies. This deficiency is traced back to the insufficient description of dynamical effects in the correlation functional. Furthermore, it is shown that the xc potential used to obtain the ground state is the key factor to get reasonable spectra, whereas the choice of the xc kernel just amounts to small, although important, quantitative changes. (C) 2001 American Institute of Physics.
引用
收藏
页码:3006 / 3014
页数:9
相关论文
共 60 条
[1]   Ab initio calculation of excitonic effects in the optical spectra of semiconductors [J].
Albrecht, S ;
Reining, L ;
Del Sole, R ;
Onida, G .
PHYSICAL REVIEW LETTERS, 1998, 80 (20) :4510-4513
[2]  
ARYASETIAWAN F, UNPUB
[3]   DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
BECKE, AD .
PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100
[4]   Optical absorption of insulators and the electron-hole interaction: An ab initio calculation [J].
Benedict, LX ;
Shirley, EL ;
Bohn, RB .
PHYSICAL REVIEW LETTERS, 1998, 80 (20) :4514-4517
[5]   Real-space, real-time method for the dielectric function [J].
Bertsch, GF ;
Iwata, JI ;
Rubio, A ;
Yabana, K .
PHYSICAL REVIEW B, 2000, 62 (12) :7998-8002
[6]  
BERTSCH GF, PHYSICS0003090
[7]   PHOTOELECTRON-SPECTRA AND MOLECULAR-PROPERTIES .51. IONIZATION-POTENTIALS OF SILANES SINH2N+2 [J].
BOCK, H ;
ENSSLIN, W ;
FEHER, F ;
FREUND, R .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (03) :668-674
[8]  
Casida M. E., 1995, RECENT ADV DENSITY F, V1, P155, DOI [10.1142/9789812830586_0005, DOI 10.1142/9789812830586_0005]
[9]   Asymptotic correction approach to improving approximate exchange-correlation potentials: Time-dependent density-functional theory calculations of molecular excitation spectra [J].
Casida, ME ;
Salahub, DR .
JOURNAL OF CHEMICAL PHYSICS, 2000, 113 (20) :8918-8935
[10]  
Castro A, UNPUB