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Title: Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark

Abstract

Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and 3 transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 x 10{sup 4} deg cm{sup 2} dmol{sup -1}. The performance of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LR-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LR-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.

Authors:
; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1028549
Report Number(s):
PNNL-SA-80682
26690; KP1704020; TRN: US201122%%390
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A
Additional Journal Information:
Journal Volume: 115; Journal Issue: 40
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BENCHMARKS; FUNCTIONALS; PERFORMANCE; ROTATION; TRANSITION ELEMENTS; Time-Dependent Density Functional Theory; computations; Environmental Molecular Sciences Laboratory

Citation Formats

Srebro, Monika, Govind, Niranjan, De Jong, Wibe A, and Autschbach, Jochen. Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark. United States: N. p., 2011. Web. doi:10.1021/jp2055409.
Srebro, Monika, Govind, Niranjan, De Jong, Wibe A, & Autschbach, Jochen. Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark. United States. https://doi.org/10.1021/jp2055409
Srebro, Monika, Govind, Niranjan, De Jong, Wibe A, and Autschbach, Jochen. 2011. "Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark". United States. https://doi.org/10.1021/jp2055409.
@article{osti_1028549,
title = {Optical Rotation Calculated with Time-Dependent Density Functional Theory: The OR45 Benchmark},
author = {Srebro, Monika and Govind, Niranjan and De Jong, Wibe A and Autschbach, Jochen},
abstractNote = {Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and 3 transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 x 10{sup 4} deg cm{sup 2} dmol{sup -1}. The performance of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LR-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LR-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.},
doi = {10.1021/jp2055409},
url = {https://www.osti.gov/biblio/1028549}, journal = {Journal of Physical Chemistry A},
number = 40,
volume = 115,
place = {United States},
year = {Thu Oct 13 00:00:00 EDT 2011},
month = {Thu Oct 13 00:00:00 EDT 2011}
}