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    Benchmarking Density Functional Theory Approaches for the Description of Symmetry-Breaking in Long Polymethine Dyes

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    Type
    Article
    Authors
    Gieseking, Rebecca L.
    Ravva, Mahesh Kumar cc
    Coropceanu, Veaceslav cc
    Bredas, Jean-Luc cc
    KAUST Department
    KAUST Solar Center (KSC)
    Laboratory for Computational and Theoretical Chemistry of Advanced Materials
    Material Science and Engineering Program
    Physical Science and Engineering (PSE) Division
    Date
    2016-05-04
    Online Publication Date
    2016-05-04
    Print Publication Date
    2016-05-12
    Permanent link to this record
    http://hdl.handle.net/10754/608228
    
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    Abstract
    Long polymethines are well-known experimentally to symmetry-break, which dramatically modifies their linear and nonlinear optical properties. Computational modeling could be very useful to provide insight into the symmetry-breaking process, which is not readily available experimentally; however, accurately predicting the crossover point from symmetric to symmetry-broken structures has proven challenging. Here, we benchmark the accuracy of several DFT approaches relative to CCSD(T) geometries. In particular, we compare analogous hybrid and long-range corrected (LRC) functionals to clearly show the influence of the functional exchange term. Although both hybrid and LRC functionals can be tuned to reproduce the CCSD(T) geometries, the LRC functionals are better performing at reproducing the geometry evolution with chain length and provide a finite upper limit for the gas-phase crossover point; these methods also provide good agreement with the experimental crossover points for more complex polymethines in polar solvents. Using an approach based on LRC functionals, a reduction in the crossover length is found with increasing medium dielectric constant, which is related to localization of the excess charge on the end groups. Symmetry-breaking is associated with the appearance of an imaginary frequency of b2 symmetry involving a large change in the degree of bond-length alternation. Examination of the IR spectra show that short, isolated streptocyanines have a mode at ~1200 cm-1 involving a large change in bond-length alternation; as the polymethine length or the medium dielectric increases, the frequency of this mode decreases before becoming imaginary at the crossover point.
    Citation
    Benchmarking Density Functional Theory Approaches for the Description of Symmetry-Breaking in Long Polymethine Dyes 2016 The Journal of Physical Chemistry C
    Sponsors
    This work was primarily supported by the National Institute of Neurological Disorders and Stroke of the National Institutes of Health under Award Number R21NS084353. We acknowledge stimulating discussions with Drs. T. Körzdörfer, S.R. Marder, and J.W. Perry.
    Publisher
    American Chemical Society (ACS)
    Journal
    The Journal of Physical Chemistry C
    DOI
    10.1021/acs.jpcc.6b02100
    Additional Links
    http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.6b02100
    ae974a485f413a2113503eed53cd6c53
    10.1021/acs.jpcc.6b02100
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Material Science and Engineering Program; KAUST Solar Center (KSC)

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