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

Bibliographische Detailangaben
Veröffentlicht in:	Journal of computational chemistry. - 1984. - 39(2018), 28 vom: 30. Okt., Seite 2350-2359
1. Verfasser:	Xu, Lihua (VerfasserIn)
Weitere Verfasser:	Kumar, Anshuman, Wong, Bryan M
Format:	Online-Aufsatz
Sprache:	English
Veröffentlicht:	2018
Zugriff auf das übergeordnete Werk:	Journal of computational chemistry
Schlagworte:	Journal Article CCSD(T) DFT broken-symmetry hyperpolarizability polarizability

Beschreibung
Zusammenfassung:	© 2018 Wiley Periodicals, Inc. 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
Beschreibung:	Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE
ISSN:	1096-987X
DOI:	10.1002/jcc.25519