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

Abstract

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.

Authors:
 [1];  [1]; ORCiD logo [1]
  1. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1612454
Alternate Identifier(s):
OSTI ID: 1479533
Grant/Contract Number:  
SC0016269
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Computational Chemistry
Additional Journal Information:
Journal Volume: 39; Journal Issue: 28; Journal ID: ISSN 0192-8651
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; polarizability; hyperpolarizability; broken-symmetry; DFT; CCSD(T)

Citation Formats

Xu, Lihua, Kumar, Anshuman, and Wong, Bryan M. Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks. United States: N. p., 2018. Web. doi:10.1002/jcc.25519.
Xu, Lihua, Kumar, Anshuman, & Wong, Bryan M. Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks. United States. https://doi.org/10.1002/jcc.25519
Xu, Lihua, Kumar, Anshuman, and Wong, Bryan M. Wed . "Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks". United States. https://doi.org/10.1002/jcc.25519. https://www.osti.gov/servlets/purl/1612454.
@article{osti_1612454,
title = {Linear polarizabilities and second hyperpolarizabilities of streptocyanines: Results from broken-Symmetry DFT and new CCSD(T) benchmarks},
author = {Xu, Lihua and Kumar, Anshuman and Wong, Bryan M.},
abstractNote = {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.},
doi = {10.1002/jcc.25519},
journal = {Journal of Computational Chemistry},
number = 28,
volume = 39,
place = {United States},
year = {Wed Oct 03 00:00:00 EDT 2018},
month = {Wed Oct 03 00:00:00 EDT 2018}
}

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