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Benchmarking Post-Hartree-Fock Methods To Describe the Nonlinear Optical Properties of Polymethines: An Investigation of the Accuracy of Algebraic Diagrammatic Construction (ADC) Approaches
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0002-4527-2566
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2016 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 12, no 11, 5465-5476 p.Article in journal (Refereed) Published
Abstract [en]

Third-order nonlinear optical (NLO) properties of polymethine dyes have been widely studied for applications such as all-optical switching. However, the limited accuracy of the current computational methodologies has prevented a comprehensive understanding of the nature of the lowest excited states and their influence on the molecular optical and NLO properties. Here, attention is paid to the lowest excited-state energies and their energetic ratio, as these characteristics impact the figure-of-merit for all-optical switching. For a series of model polymethines, we compare several algebraic diagrammatic construction (ADC) schemes for the polarization propagator with approximate second-order coupled cluster (CC2) theory, the widely used INDO/MRDCI approach and the symmetry adapted cluster configuration interaction (SAC-CI) algorithm incorporating singles and doubles linked excitation operators (SAC-CI SD-R). We focus in particular on the ground-to-excited state transition dipole moments and the corresponding state dipole moments, since these quantities are found to be of utmost importance for an effective description of the third-order polarizability gamma and two-photon absorption spectra. A sum-overstates expression has been used, which is, found to quickly converge. While ADC(3/2) has been found to be the most appropriate method to calculate these properties, CC2 performs poorly.

Place, publisher, year, edition, pages
American Chemical Society , 2016. Vol. 12, no 11, 5465-5476 p.
National Category
Chemical Sciences
URN: urn:nbn:se:kth:diva-197779DOI: 10.1021/acs.jctc.6b00615ISI: 000387519400022ScopusID: 2-s2.0-84994700971OAI: diva2:1060240

QC 20161228

Available from: 2016-12-28 Created: 2016-12-08 Last updated: 2016-12-28Bibliographically approved

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