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J Chem Theory Comput. 2013 Nov 12;9(11):4991-5003. doi: 10.1021/ct400649r. Epub 2013 Oct 15.

Longest-Wavelength Electronic Excitations of Linear Cyanines: The Role of Electron Delocalization and of Approximations in Time-Dependent Density Functional Theory.

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Department of Chemistry, University at Buffalo, State University of New York , Buffalo, New York 14260-3000, United States.


The lowest-energy/longest-wavelength electronic singlet excitation energies of linear cyanine dyes are examined, using time-dependent density functional theory (TDDFT) and selected wave function methods in comparison with literature data. Variations of the bond-length alternation obtained with different optimized structures produce small differences of the excitation energy in the limit of an infinite chain. Hybrid functionals with range-separated exchange are optimally 'tuned', which is shown to minimize the delocalization error (DE) in the cyanine π systems. Much unlike the case of charge-transfer excitations, small DEs are not strongly correlated with better performance. A representative cyanine is analyzed in detail. Compared with accurate benchmark data, TDDFT with 'pure' local functionals gives too high singlet excitation energies for all systems, but DFT-based ΔSCF calculations with a local functional severely underestimates the energies. TDDFT strongly overestimates the difference between singlet and triplet excitation energies. An analysis points to systematically much too small magnitudes of integrals from the DFT components of the exchange-correlation response kernel as the likely culprit. The findings support previous suggestions that the differential correlation energy between the ground and excited state is not correctly produced by TDDFT with most functionals.


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