Theoretical Chemistry Accounts

, 124:395 | Cite as

Electronic structure and optical properties of chelating heteroatomic conjugated molecules: a SAC-CI study

  • Yun-Peng Lu
  • Masahiro EharaEmail author
Regular Article


The electronic structure and optical properties of 13 chelating heteroatomic conjugated molecules such as pyridine, benzoxazole, and benzothiazole derivatives, which are used as C–N ligands in organometallic compounds, have been investigated. The geometries of the ground and first excited states were obtained by the DFT and CIS methods, respectively, followed by the SAC-CI calculations of the transition energies for absorption and emission. For six compounds whose experimental data are available, the SAC-CI calculations reproduced the experimental values satisfactorily with deviations of less than 0.3 eV for absorption and 0.1 eV for emission except for benzoxazoles. For other molecules, the theoretical absorption and emission spectra were predicted. The lowest ππ* excited-state geometries was calculated to be planar for most of the molecules with two or three conjugated rings connected by single bond. The geometry change due to the ππ* excitation was qualitatively interpreted by electrostatic force theory based on SAC/SAC-CI electron density difference. The excitations are relatively localized in the central region and in the lowest ππ* excited state, the inter-ring single bond shows large change, with a contraction of 0.05–0.09 Å. The present calculations provide reliable information regarding the energy levels of these chelating heteroatomic conjugated compounds.


Ab initio SAC-CI Heteroatomic conjugated molecules Optical properties Electronic structure 



The authors would like to thank Dr. R. Fukuda and Prof. H. Nakatsuji for the direct SAC-CI program code. They also thank the reviewers for the valuable comments. This study was supported by the JSPS Exchange Program for East Asian Young Researchers. M.E. was supported by the grant from the JST-CREST, Scientific Research in Priority Areas “Molecular Theory for Real Systems” from the Ministry of Education, Culture, Sports, Science and Technology of Japan, the Next Generation Supercomputing Project, and the Molecular-Based New Computational Science Program, NINS. A part of the computations were performed at Research Center for Computational Science, Okazaki, Japan.

Supplementary material

214_2009_629_MOESM1_ESM.pdf (130 kb)
Supplementary material 1 (PDF 130 kb)


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Copyright information

© Springer-Verlag 2009

Authors and Affiliations

  1. 1.Division of Chemistry and Biochemistry, School of Physical and Mathematical SciencesNanyang Technological UniversitySingaporeSingapore
  2. 2.Institute for Molecular ScienceOkazakiJapan
  3. 3.JST-CRESTTokyoJapan

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