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Phys Chem Chem Phys. 2009 Jun 14;11(22):4498-508. doi: 10.1039/b901743g. Epub 2009 Apr 24.

Absorption and fluorescence properties of oligothiophene biomarkers from long-range-corrected time-dependent density functional theory.

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  • 1Materials Chemistry Department, Sandia National Laboratories, Livermore, California 94551, USA. bmwong@sandia.gov

Abstract

The absorption and fluorescence properties in a class of oligothiophene push-pull biomarkers are investigated with a long-range-corrected (LC) density functional method. Using linear-response time-dependent density functional theory (TDDFT), we calculate excitation energies, fluorescence energies, oscillator strengths, and excited-state dipole moments. To benchmark and assess the quality of the LC-TDDFT formalism, an extensive comparison is made between LC-BLYP excitation energies and approximate coupled cluster singles and doubles (CC2) calculations. When using a properly-optimized value of the range parameter, mu, we find that the LC technique provides an accurate description of charge-transfer excitations as a function of biomarker size and chemical functionalization. In contrast, we find that re-optimizing the fraction of Hartree Fock exchange in conventional hybrid functionals still yields an inconsistent description of excitation energies and oscillator strengths for the two lowest excited states in our series of biomarkers. The results of the present study emphasize the importance of a distance-dependent contribution of exchange in TDDFT for investigating excited-state properties.

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