Acta Phys. -Chim. Sin. ›› 2010, Vol. 26 ›› Issue (02): 447-452.doi: 10.3866/PKU.WHXB20100144

• QUANTUM CHEMISTRY AND COMPUTATION CHEMISTRY • Previous Articles     Next Articles

Effect of Alkyl Substitution on the Electronic Structure and Spectrum of Rhodamine

LEI Yong-Lin, HUO Ji-Chuan   

  1. College of Material Science and Engineering, Southwest University of Science and Technology, Mianyang 621010, Sichuan Province, P. R. China
  • Received:2009-06-22 Revised:2009-09-28 Published:2010-01-26
  • Contact: HUO Ji-Chuan E-mail:huojichuan@swust.edu.cn

Abstract:

The structures of eight kinds of rhodamine compounds, substituted by different alkyls at different positions, were optimized using the density functional theory (DFT) at the B3LYP level. On the basis of these optimized structures, the influence of the substituting group on the electronic structures and spectral properties as well as frontier molecular orbitals of rhodamine were analyzed using the singlet configuration interaction (CIS) method and time dependent density functional theory (TD-DFT). Results indicate that the frontier molecular orbitals are mainly distributed in the xanthene ring of rhodamine when only one H atom of the two N-ends in the rhodamine molecule is substituted by alkyls. The distribution of the highest occupied molecular orbital (HOMO) is the greatest in the main conjugate ring and the difference in the distribution ratio between the HOMO and the the lowest unoccupied molecular orbital LUMO) is small. When the four H atoms of the two N-ends in the rhodamine molecules are substituted by methyl, the bandgap is found to be the narrowest and the red shift in the gas maximum absorption wavelength is the largest. When the four H atoms of the two N-ends in rhodamine molecules are substituted by ethyl, the gas fluorescence maximum emission wavelength is the longest.

Key words: Density functional theory, Rhodamine, Alkyl substitution, Frontier molecular orbital, Electronic spectrum

MSC2000: 

  • O641