First principles crystal engineering of nonlinear optical materials. I. Prototypical case of urea

Masunov, A.E.; Tannu, A.; Dyakov, A.A.; Matveeva, A.D.; Freidzon, A.Y.; Odinokov, A.V.; Bagaturyants, A.A.

Авторы: Masunov Artëm E., Tannu Arman, Dyakov Alexander A., Matveeva Anastasia D., Freidzon Alexandra Ya, Odinokov Alexey V., Bagaturyants Alexander A.
Журнал: Journal of Chemical Physics
Том: 146
Номер: 24
Год издания: 2017
Издательство: AIP Publishing
Местоположение издательства: United States
Первая страница: 244104
DOI: 10.1063/1.4986793
Аннотация: The crystalline materials with nonlinear optical (NLO) properties are critically important for several technological applications, including nanophotonic and second harmonic generation devices. Urea is often considered to be a standard NLO material, due to the combination of non-centrosymmetric crystal packing and capacity for intramolecular charge transfer. Various approaches to crystal engineering of non-centrosymmetric molecular materials were reported in the literature. Here we propose using global lattice energy minimization to predict the crystal packing from the first principles. We developed a methodology that includes the following: (1) parameter derivation for polarizable force field AMOEBA; (2) local minimizations of crystal structures with these parameters, combined with the evolutionary algorithm for a global minimum search, implemented in program USPEX; (3) filtering out duplicate polymorphs produced; (4) reoptimization and final ranking based on density functional theory (DFT) with many-body dispersion (MBD) correction; and (5) prediction of the second-order susceptibility tensor by finite field approach. This methodology was applied to predict virtual urea polymorphs. After filtering based on packing similarity, only two distinct packing modes were predicted: one experimental and one hypothetical. DFT + MBD ranking established non-centrosymmetric crystal packing as the global minimum, in agreement with the experiment. Finite field approach was used to predict nonlinear susceptibility, and H-bonding was found to account for a 2.5-fold increase in molecular hyperpolarizability to the bulk value.
Добавил в систему: Фрейдзон Александра Яковлевна

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First principles crystal engineering of nonlinear optical materials. I. Prototypical case of ureaстатья