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Experimental benchmark data and systematic evaluation of two a posteriori, polarizable-continuum corrections for vertical excitation energies in solution.

J.-M. Mewes, Z.-Q. You, M. Wormit, T. Kriesche, J. M. Herbert, and A. Dreuw
J. Phys. Chem. A 119, 5446–5464 (2015)

Abstract

We report the implementation and evaluation of a perturbative, density-based correction scheme for vertical excitation energies calculated in the framework of a polarizable continuum model (PCM). In this work, we make use of the algebraic-diagrammatic construction (ADC) scheme of up to third order as well as time-dependent density-functional theory (TD-DFT) to demonstrate the approach. Since the proposed first-order correction terms depend solely the zeroth-order excited-state density, a transfer of the approach to any other configuration interaction-type excited-state method is straightforward. For the evaluation of the method, we assembled a set of experimental benchmark data for solvatochromism in molecules (xBDSM) containing 44 gas-phase to solvent shifts for 17 molecules. These data are compared to solvent-shifts calculated at the ADC(1), ADC(2), ADC(3/2) and TD-DFT/LRC-ωPBE levels of theory in combination with state-specific as well as linear-response type PCM-based correction schemes. Some unexpected trends and differences between TD-DFT, the levels of ADC, and variants of the PCM are observed and discussed. The most accurate combinations reproduce experimental solvent-shifts resulting from the bulk electrostatic interaction with maximum errors in the order of 50 meV and a mean absolute deviation of 20–30 meV for the xBDSM set.

[DOI] [PDF]
[Supporting Information: Part 1, Part 2, Part 3, Part 4, Part 5]
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