title: Density functional study of tetraphenylporphyrin long-range exciton coupling.
abstract: The performance of time-dependent density functional theory (TDDFT) for calculations of long-range exciton circular dichroism (CD) is investigated. Tetraphenylporphyrin (TPP) is used as a representative of a class of strongly absorbing chromophores for which exciton CD with chromophore separations of 50 Å and even beyond has been observed experimentally. A dimer model for TPP is set up to reproduce long-range exciton CD previously observed for a brevetoxin derivative. The calculated CD intensity is consistent with TPP separations of over 40 Å. It is found that a hybrid functional with fully long-range corrected range-separated exchange performs best for full TDDFT calculations of the dimer. The range-separation parameter is optimally tuned for TPP, resulting in a good quality TPP absorption spectrum and small DFT delocalization error (measured by the curvature of the energy calculated as a function of fractional electron numbers). Calculated TDDFT data for the absorption spectra of TPP are also used as input for a 'matrix method' (MM) model of the exciton CD. For long-range exciton CD, comparison of MM spectra with full TDDFT CD spectra for the dimer shows that the matrix method is capable of producing very accurate results. A MM spectrum obtained from TPP absorption data calculated with the nonhybrid Becke88-Perdew86 (BP) functional is shown to match the experimental brevetoxin spectrum 'best', but for the wrong reasons.
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York 312 Natural Sciences Complex, Buffalo, NY 14260-3000 (USA) E-mail: jochena@buffalo.edu.
authors.forename: Barry
authors.initials: B
authors.lastname: Moore
authors.affiliation: Department of Chemistry, University at Buffalo, State University of New York 312 Natural Sciences Complex, Buffalo, NY 14260-3000 (USA) E-mail: jochena@buffalo.edu.
authors.forename: Jochen
authors.initials: J
authors.lastname: Autschbach
keywords: CD/LC/ORD; ab initio calculations; density-functional calculations; long-range exciton circular dichroism; porphyrins