Benchmarking Post-Hartree–Fock Methods To Describe the Nonlinear Optical Properties of Polymethines: An Investigation of the Accuracy of Algebraic Diagrammatic Construction (ADC) Approaches

Handle URI:
http://hdl.handle.net/10754/622380
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
Authors:
Knippenberg, Stefan; Gieseking, Rebecca L.; Rehn, Dirk R.; Mukhopadhyay, Sukrit; Dreuw, Andreas; Bredas, Jean-Luc ( 0000-0001-7278-4471 )
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.
KAUST Department:
Physical Sciences and Engineering (PSE) Division
Citation:
Knippenberg S, Gieseking RL, Rehn DR, Mukhopadhyay S, Dreuw A, et al. (2016) Benchmarking Post-Hartree–Fock Methods To Describe the Nonlinear Optical Properties of Polymethines: An Investigation of the Accuracy of Algebraic Diagrammatic Construction (ADC) Approaches. Journal of Chemical Theory and Computation 12: 5465–5476. Available: http://dx.doi.org/10.1021/acs.jctc.6b00615.
Publisher:
American Chemical Society (ACS)
Journal:
Journal of Chemical Theory and Computation
Issue Date:
7-Oct-2016
DOI:
10.1021/acs.jctc.6b00615
Type:
Article
ISSN:
1549-9618; 1549-9626
Sponsors:
S.K. is grateful to the Georgia Institute of Technology for their hospitality in Fall 2012. The authors thank Dr. Paul Winget for computational assistance.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b00615
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorKnippenberg, Stefanen
dc.contributor.authorGieseking, Rebecca L.en
dc.contributor.authorRehn, Dirk R.en
dc.contributor.authorMukhopadhyay, Sukriten
dc.contributor.authorDreuw, Andreasen
dc.contributor.authorBredas, Jean-Lucen
dc.date.accessioned2017-01-02T09:28:27Z-
dc.date.available2017-01-02T09:28:27Z-
dc.date.issued2016-10-07en
dc.identifier.citationKnippenberg S, Gieseking RL, Rehn DR, Mukhopadhyay S, Dreuw A, et al. (2016) Benchmarking Post-Hartree–Fock Methods To Describe the Nonlinear Optical Properties of Polymethines: An Investigation of the Accuracy of Algebraic Diagrammatic Construction (ADC) Approaches. Journal of Chemical Theory and Computation 12: 5465–5476. Available: http://dx.doi.org/10.1021/acs.jctc.6b00615.en
dc.identifier.issn1549-9618en
dc.identifier.issn1549-9626en
dc.identifier.doi10.1021/acs.jctc.6b00615en
dc.identifier.urihttp://hdl.handle.net/10754/622380-
dc.description.abstractThird-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.en
dc.description.sponsorshipS.K. is grateful to the Georgia Institute of Technology for their hospitality in Fall 2012. The authors thank Dr. Paul Winget for computational assistance.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jctc.6b00615en
dc.titleBenchmarking Post-Hartree–Fock Methods To Describe the Nonlinear Optical Properties of Polymethines: An Investigation of the Accuracy of Algebraic Diagrammatic Construction (ADC) Approachesen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalJournal of Chemical Theory and Computationen
dc.contributor.institutionDivision of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, Roslagstullsbacken 15, S-106 91 Stockholm, Swedenen
dc.contributor.institutionSchool of Chemistry and Biochemistry and Center for Organic Materials for All-Optical Switching (COMAS), Georgia Institute of Technology, Atlanta, Georgia 30332-0400, United Statesen
dc.contributor.institutionDepartment of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United Statesen
dc.contributor.institutionDepartment of Physics, Chemistry and Biology, Linköping University, S-581 83 Linköping, Swedenen
dc.contributor.institutionInterdisciplinary Center for Scientific Computing, Ruprecht-Karls University, Im Neuenheimer Feld 205, 69120 Heidelberg, Germanyen
kaust.authorBredas, Jean-Lucen
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