Calculation of linear and nonlinear optical properties of azobenzene derivatives with Kohn–Sham and coupled-cluster methods

Literature Information

Publication Date 2018-02-06
DOI 10.1039/C7CP08655E
Impact Factor 3.676
Authors

Arun K. Pal, Thomas J. Duignan, Jochen Autschbach


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Abstract

Linear polarizabilities (α) and second hyperpolarizabilities (γ) of unsubstituted azobenzenes and ‘push–pull’ azobenzene derivatives are investigated using Kohn–Sham theory (KST) and coupled-cluster (CC) approaches. Various standard exchange–correlation functionals as well as a non-empirically ‘tuned’ long-range corrected (LC) functional with range-separated exchange are used in the KST calculations. When compared to correlated ab initio calculations and measurements, the tuned functional gives accurate low-energy excitation energies, especially for charge transfer (CT) transitions, and performs well for α. Basis set and solvent effects are also studied. In contrast to expectations, but in agreement with a prior study of π-conjugated systems that do not have low-energy CT excitations, the improvements of the CT excitation energies for the push–pull π-chromophores due to tuning do not go along with clear improvements of γ toward the CC reference data, likely due to the importance of the dynamic electron correlation for this property.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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