Impact of van der Waals interactions on the structural and nonlinear optical properties of azobenzene switches
文献信息
Frédéric Castet
The geometrical structures, relative Z–E energies, and second-order nonlinear responses of a collection of azobenzene molecules symmetrically substituted in the meta-position with functional groups of different bulkiness are investigated using various ab initio and density functional approximations. We show that RI-MP2 and RI-CC2 approximations provide very similar geometries and relative energies and evidence that London dispersion interactions existing between bulky meta-substituents stabilize the Z conformer. The ωB97X-D exchange–correlation functional provides an accurate description of these effects and gives a good account of the nonlinear optical response of the molecules. We show that density functional approximations should include no less than 50% of Hartree–Fock exchange to provide accurate hyperpolarizabilities. A property–structure analysis of the azobenzene derivatives reveals that the main contribution to the first hyperpolarizability comes from the azo bond, but phenyl meso-substituents can enhance it.
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Physical Chemistry Chemical Physics

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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