A TD-DFT basis set and density functional assessment for the calculation of electronic excitation energies of fluorene

Cristina Aparecida Barboza, Pedro Antonio Muniz Vazquez, Desmond Mac-Leod Carey, Ramiro Arratia-Perez

Research output: Contribution to journalArticlepeer-review

29 Citations (Scopus)

Abstract

Conjugated organic materials are the subject of intensive research for a range of optoelectronic applications. A model for such molecules is fluorene, which consists of rigid planar biphenyl units of C2v symmetry. A low energy experimental absorption spectrum in the gas phase is composed of A 1 and B2 transitions. The aim of this work is to evaluate the performance of the basis sets cc-pVXZ (X = D and T), aug-cc-pVDZ, 6-31G**, 6-31++G**, 6-311G**, 6-311++G**, Sadlej-pVTZ, Z2Pol, Z3Pol, and pSBKJC and of the functionals B3LYP, B3LYP/CS00, CAM-B3LYP, PBE0, and LB94 in predicting the electronic transitions obtained taking linear response-coupled cluster singles and doubles (LR-CCSD) results as the theoretical reference. Our findings suggest that the time-dependent density functional theory singles method is not able to correctly assign the predicted spectrum while LR-CCSD always correctly describes the experimental data. Among the studied density functionals, the best performance was achieved by the CAMB3LYP. For transitions above 5 eV, diffuse functions are required to properly predict the observed transitions.

Original languageEnglish
Pages (from-to)3434-3438
Number of pages5
JournalInternational Journal of Quantum Chemistry
Volume112
Issue number20
DOIs
Publication statusPublished - 15 Oct 2012

Keywords

  • LR-CCSD
  • TD-DFT
  • dendrogram
  • excitation energies
  • fluorene
  • principal component analysis

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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