title: Benchmarking Post-Hartree-Fock Methods To Describe the Nonlinear Optical Properties of Polymethines: An Investigation of the Accuracy of Algebraic Diagrammatic Construction (ADC) Approaches.
abstract: 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 γ 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.
authors.affiliation: Division of Theoretical Chemistry and Biology, KTH Royal Institute of Technology , Roslagstullsbacken 15, S-106 91 Stockholm, Sweden.
authors.forename: Stefan
authors.initials: S
authors.lastname: Knippenberg
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Materials for All-Optical Switching (COMAS), Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.|Department of Chemistry, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208, United States.
authors.forename: Rebecca L
authors.initials: RL
authors.lastname: Gieseking
authors.affiliation: Department of Physics, Chemistry and Biology, Linköping University , S-581 83 Linköping, Sweden.
authors.forename: Dirk R
authors.initials: DR
authors.lastname: Rehn
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Materials for All-Optical Switching (COMAS), Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.
authors.forename: Sukrit
authors.initials: S
authors.lastname: Mukhopadhyay
authors.affiliation: Interdisciplinary Center for Scientific Computing, Ruprecht-Karls University , Im Neuenheimer Feld 205, 69120 Heidelberg, Germany.
authors.forename: Andreas
authors.initials: A
authors.lastname: Dreuw
authors.affiliation: School of Chemistry and Biochemistry and Center for Organic Materials for All-Optical Switching (COMAS), Georgia Institute of Technology , Atlanta, Georgia 30332-0400, United States.|Physical Science and Engineering Division, King Abdullah University of Science and Technology , Thuwal 23955-6900, Kingdom of Saudi Arabia.
authors.forename: Jean-Luc
authors.initials: JL
authors.lastname: Brédas