Influence of the exchange-correlation potential in density-functional calculations on polarizabilities and absorption spectra of alkali-metal clusters

被引:38
作者
van Gisbergen, SJA
Pacheco, JM
Baerends, EJ
机构
[1] Vrije Univ Amsterdam, Sci Comp & Modelling NV, Theoret Chem Sect, NL-1081 HV Amsterdam, Netherlands
[2] Univ Coimbra, Dept Fis, P-3004516 Coimbra, Portugal
来源
PHYSICAL REVIEW A | 2001年 / 63卷 / 06期
关键词
D O I
10.1103/PhysRevA.63.063201
中图分类号
O43 [光学];
学科分类号
070207 ; 0803 ;
摘要
All-electron calculations in large basis sets of excitation energies, oscillator strengths, and polarizabilities of small alkali-metal clusters of Li, Na, and K, with up to eight atoms, are performed using time-dependent density-functional theory. It is shown that the use of the recently developed statistical average of orbital potentials (SAOP) exchange-correlation (chic) potential [P.R.T. Schipper et al., J. Chem. Phys. 112, 1344 (2000)] leads to polarizabilities of these alkali-metal clusters which are 10-15% larger than polarizabilities calculated with the re potential of the local-density approximation (LDA). The lower LDA polarizabilities (in comparison to the SAOP) are shown to originate from differences in the low-lying excitation energies, which are determined by the re potential in the molecular inner and valence region. In spite of such differences, both SAOP and LDA results are shown to provide reliable assignments of the experimental absorption spectra, with typical errors in peak positions of only 0.1-0.2 eV, or even less.
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页数:15
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共 61 条
[51]   Implementation of time-dependent density functional response equations [J].
van Gisbergen, SJA ;
Snijders, JG ;
Baerends, EJ .
COMPUTER PHYSICS COMMUNICATIONS, 1999, 118 (2-3) :119-138
[52]   Density-functional-theory response-property calculations with accurate exchange-correlation potentials [J].
van Gisbergen, SJA ;
Kootstra, F ;
Schipper, PRT ;
Gritsenko, OV ;
Snijders, JG ;
Baerends, EJ .
PHYSICAL REVIEW A, 1998, 57 (04) :2556-2571
[53]   A DENSITY-FUNCTIONAL THEORY STUDY OF FREQUENCY-DEPENDENT POLARIZABILITIES AND VAN-DER-WAALS DISPERSION COEFFICIENTS FOR POLYATOMIC-MOLECULES [J].
VANGISBERGEN, SJA ;
SNIJDERS, JG ;
BAERENDS, EJ .
JOURNAL OF CHEMICAL PHYSICS, 1995, 103 (21) :9347-9354
[54]   Improved density functional theory results for frequency-dependent polarizabilities, by the use of an exchange-correlation potential with correct asymptotic behavior [J].
vanGisbergen, SJA ;
Osinga, VP ;
Gritsenko, OV ;
vanLeeuwen, R ;
Snijders, JG ;
Baerends, EJ .
JOURNAL OF CHEMICAL PHYSICS, 1996, 105 (08) :3142-3151
[55]   EXCHANGE-CORRELATION POTENTIAL WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].
VANLEEUWEN, R ;
BAERENDS, EJ .
PHYSICAL REVIEW A, 1994, 49 (04) :2421-2431
[56]   RELATIVISTIC REGULAR 2-COMPONENT HAMILTONIANS [J].
VANLENTHE, E ;
BAERENDS, EJ ;
SNIJDERS, JG .
JOURNAL OF CHEMICAL PHYSICS, 1993, 99 (06) :4597-4610
[57]   Ab initio excitation spectra and collective electronic response in atoms and clusters [J].
Vasiliev, I ;
Ögüt, S ;
Chelikowsky, JR .
PHYSICAL REVIEW LETTERS, 1999, 82 (09) :1919-1922
[58]   ACCURATE SPIN-DEPENDENT ELECTRON LIQUID CORRELATION ENERGIES FOR LOCAL SPIN-DENSITY CALCULATIONS - A CRITICAL ANALYSIS [J].
VOSKO, SH ;
WILK, L ;
NUSAIR, M .
CANADIAN JOURNAL OF PHYSICS, 1980, 58 (08) :1200-1211
[59]   MOLECULAR EXCITED-STATES VERSUS COLLECTIVE ELECTRONIC OSCILLATIONS - OPTICAL-ABSORPTION PROBES OF NA4 AND NA8 [J].
WANG, CRC ;
POLLACK, S ;
KAPPES, MM .
CHEMICAL PHYSICS LETTERS, 1990, 166 (01) :26-31
[60]  
WANG CRC, 1990, J CHEM PHYS, V93, P3787, DOI 10.1063/1.458765