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

Abstract

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 tomore » predict nonlinear susceptibility, and H-bonding was found to account for a 2.5-fold increase in molecular hyperpolarizability to the bulk value.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [4];  [5]; ORCiD logo [4]
  1. Univ. of Central Florida, Orlando, FL (United States); South Ural State Univ., Chelyabinsk (Russian Federation); Moscow Engineering Physics Inst., Moscow (Russian Federation); Russian Academy of Sciences (RAS), Moscow (Russian Federation)
  2. Univ. of Central Florida, Orlando, FL (United States)
  3. South Ural State Univ., Chelyabinsk (Russian Federation)
  4. Moscow Engineering Physics Inst., Moscow (Russian Federation); Russian Academy of Sciences (RAS), Moscow (Russian Federation)
  5. Russian Academy of Sciences (RAS), Moscow (Russian Federation)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1497849
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Masunov, Artëm E., Tannu, Arman, Dyakov, Alexander A., Matveeva, Anastasia D., Freidzon, Alexandra Ya., Odinokov, Alexey V., and Bagaturyants, Alexander A. First principles crystal engineering of nonlinear optical materials. I. Prototypical case of urea. United States: N. p., 2017. Web. doi:10.1063/1.4986793.
Masunov, Artëm E., Tannu, Arman, Dyakov, Alexander A., Matveeva, Anastasia D., Freidzon, Alexandra Ya., Odinokov, Alexey V., & Bagaturyants, Alexander A. First principles crystal engineering of nonlinear optical materials. I. Prototypical case of urea. United States. doi:10.1063/1.4986793.
Masunov, Artëm E., Tannu, Arman, Dyakov, Alexander A., Matveeva, Anastasia D., Freidzon, Alexandra Ya., Odinokov, Alexey V., and Bagaturyants, Alexander A. Mon . "First principles crystal engineering of nonlinear optical materials. I. Prototypical case of urea". United States. doi:10.1063/1.4986793. https://www.osti.gov/servlets/purl/1497849.
@article{osti_1497849,
title = {First principles crystal engineering of nonlinear optical materials. I. Prototypical case of urea},
author = {Masunov, Artëm E. and Tannu, Arman and Dyakov, Alexander A. and Matveeva, Anastasia D. and Freidzon, Alexandra Ya. and Odinokov, Alexey V. and Bagaturyants, Alexander A.},
abstractNote = {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.},
doi = {10.1063/1.4986793},
journal = {Journal of Chemical Physics},
number = 24,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

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Figures / Tables:

Figure 1 Figure 1: Experimental crystal structure of urea [(a) and (b)] and thiourea [(c) and (d)], both shown in two crystallographic projections.

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