Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks

Xu, Lihua; Kumar, Anshuman; Wong, Bryan M.

doi:10.1002/jcc.25519

Title: Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks

Journal Article · Wed Oct 03 00:00:00 EDT 2018 · Journal of Computational Chemistry

DOI:https://doi.org/10.1002/jcc.25519· OSTI ID:1612454

Xu, Lihua ^[1]; Kumar, Anshuman ^[1];

^[1]

Univ. of California, Riverside, CA (United States)

We present a detailed analysis of the linear polarizability ( α ) and second hyperpolarizability ( γ ) in a series of streptocyanines, as predicted with various range‐separated functionals and CCSD(T)‐based methods. Contrary to previous work on these systems, we find that the lowest‐energy electronic states for the larger streptocyanine oligomers are not closed‐shell singlets, and improved accuracy can be obtained with certain DFT methods by allowing the system to relax to a lower‐energy broken‐symmetry solution. Our extensive analyses are complemented by new large‐scale CCSD(T) and explicitly correlated CCSD(T)‐F12 calculations that comprise the most complete and accurate benchmarks of α and γ for the streptocyanine systems to date. Taken together, our CCSD(T) and broken‐symmetry DFT calculations (1) show that the MP2 benchmarks used in previous studies still exhibit significant errors (~ 25% for α and ~100% for γ ) and, therefore, the MP2 calculations should not be used as reliable benchmarks for polarizabilities or hyperpolarizabilities, and (2) emphasize the importance of testing for a lower‐energy open‐shell configuration when calculating nonlinear optical properties for these systems. © 2018 Wiley Periodicals, Inc.

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Research Organization:: Univ. of California, Riverside, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0016269

OSTI ID:: 1612454

Alternate ID(s):: OSTI ID: 1479533

Journal Information:: Journal of Computational Chemistry, Vol. 39, Issue 28; ISSN 0192-8651

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry
polarizability
hyperpolarizability
broken-symmetry
DFT
CCSD(T)

Title: Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks

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