Electronic excitation of sulfur-organic compounds - performance of time-dependent density functional theory

被引:188
作者
Fabian, J [1 ]
机构
[1] Tech Univ Dresden, Inst Organ Chem, D-01062 Dresden, Germany
关键词
sulfur-organic compounds; Dyes; time-dependent density functional theory; Zerner's intermediate neglect of differential overlap; Pariser-Parr-Pople;
D O I
10.1007/s002140100250
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
To define the scope and limitations of the time-dependent density functional theory (TDDFT) method, spectral absorption data of a series of about 100 neutral or charged sulfur-organic compounds with up to 24 non-hydrogen atoms and up to four sulfur atoms were calculated in the near-UV, visible and IR regions. although the theoretical vertical transition energies correspond only approximately to experimental absorption band maxima, the mean absolute deviation was calculated to be 0.21 eV (1600 cm(-1)). The main absorption features of various compounds with monocoordinated or dicoordinated sulfur atoms are well reproduced. As far as possible TDDFT results were compared with those of semiempirical Zerner's intermediate neglect of differential overlap (ZINDO/S) and of Pariser-Parr-Pople (PPP) calculations. TDDFT also works well in cases where the semiempirical methods fail. Limitations of TDDFT were encountered with calculations of spectral absorptions of dye molecules. The "vinylene shift" of polymethine dyes is not reproduced by TDDFT. Whereas electronic excitation energies delocalized polar and betainic chromophores are reasonably well reproduced, excitation energies of charge-transfer-type and charge-resonance-type transitions of weakly interacting composite chromophores are significantly underestimated.
引用
收藏
页码:199 / 217
页数:19
相关论文
共 168 条
[1]   STUDIES ON THE ELECTRONIC ABSORPTION-SPECTRA OF 2,2'-BITHIENYL AND SOME OF ITS DERIVATIVES - A MOLECULAR-ORBITAL TREATMENT [J].
ABUEITTAH, RH ;
ALSUGEIR, FA .
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1985, 58 (07) :2126-2132
[2]   SYNTHESIS, SPECTRA, AND REACTIONS OF SOME S-ALKYLTHIOPHENIUM SALTS [J].
ACHESON, RM ;
HARRISON, DR .
JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1970, (13) :1764-&
[3]   SYNTHESES OF CYCLOPENTA[C]THIAPYRAN AND 2-PHENYL-2-PYRINDINE [J].
ANDERSON, AG ;
HARRISON, WF ;
ANDERSON, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1963, 85 (21) :3448-&
[4]  
ANGELONI AS, 1963, ANN CHIM-ROME, V53, P1665
[5]   OPTICAL ABSORPTION SPECTRA OF TETRAMETHYL-1,3-CYCLOBUTANEDIONE AND CORRESPONDING DITHIONE [J].
BALLARD, RE ;
PARK, CH .
SPECTROCHIMICA ACTA PART A-MOLECULAR SPECTROSCOPY, 1970, A 26 (01) :43-&
[6]   EQUIVALENCE OF ENERGY GAPS DELTA-1(1,2) AND DELTA-E(1,2) BETWEEN CORRESPONDING BANDS IN PHOTOELECTRON (I) AND ELECTRONIC ABSORPTION (E) SPECTRA OF SPIRO[4.4]NONATETRAENE - AMUSING CONSEQUENCE OF SPIROCONJUGATION [J].
BATICH, C ;
HEILBRON.E ;
ROMMEL, E ;
SEMMELHA.MF ;
FOOS, JS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1974, 96 (25) :7662-7668
[7]   Calculation of excitation energies within time-dependent density functional theory using auxiliary basis set expansions [J].
Bauernschmitt, R ;
Haser, M ;
Treutler, O ;
Ahlrichs, R .
CHEMICAL PHYSICS LETTERS, 1997, 264 (06) :573-578
[8]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[9]   DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].
BECKE, AD .
JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652
[10]   PUSH-PULL POLYENES AND CAROTENOIDS - SYNTHESIS AND NON-LINEAR OPTICAL-PROPERTIES [J].
BLANCHARDDESCE, M ;
LEDOUX, I ;
LEHN, JM ;
MALTHETE, J ;
ZYSS, J .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (11) :737-739