Abstract
The mixed cation compounds Na1-xKxAsSe2 (x = 0.8, 0.65, 0.5) and Na0.1K0.9AsS2 crystallize in the polar noncentrosymmetric space group Cc. The AAsQ2 (A = alkali metals, Q = S, Se) family features one-dimensional (1D) 1/∞[AQ2-] chains comprising corner-sharing pyramidal AQ3 units in which the packing of these chains is dependent on the alkali metals. The parallel 1/∞[AQ2-] chains interact via short As···Se contacts, which increase in length when the fraction of K atoms is increased. The increase in the As···Se interchain distance increases the band gap from 1.75 eV in γ-NaAsSe2 to 2.01 eV in Na0.35K0.65AsSe2, 2.07 eV in Na0.2K0.8AsSe2, and 2.18 eV in Na0.1K0.9AsS2. The Na1-xKxAsSe2 (x = 0.8, 0.65) compounds melt congruently at approximately 316 °C. Wavelength-dependent second harmonic generation (SHG) measurements on powder samples of Na1-xKxAsSe2 (x = 0.8, 0.65, 0.5) and Na0.1K0.9AsS2 suggest that Na0.2K0.8AsSe2 and Na0.1K0.9AsS2 have the highest SHG response and exhibit significantly higher laser-induced damage thresholds (LIDTs). Theoretical SHG calculations on Na0.5K0.5AsSe2 confirm its SHG response with the highest value of d33 = 22.5 pm/V (χ333(2) = 45.0 pm/V). The effective nonlinearity for a randomly oriented powder is calculated to be deff = 18.9 pm/V (χeff(2) = 37.8 pm/V), which is consistent with the experimentally obtained value of deff = 16.5 pm/V (χeff(2) = 33.0 pm/V). Three-photon absorption is the dominant mechanism for the optical breakdown of the compounds under intense excitation at 1580 nm, with Na0.2K0.8AsSe2 exhibiting the highest stability.
Original language | English (US) |
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Pages (from-to) | 18204-18215 |
Number of pages | 12 |
Journal | Journal of the American Chemical Society |
Volume | 143 |
Issue number | 43 |
DOIs | |
State | Published - Nov 3 2021 |
Funding
M.G.K., V.G., A.K.I., and B.M.O. acknowledge the Air Force Office of Scientific Research Grant number FA9550-18-S-0003. The IMSERC PCM facility at Northwestern University used in this work received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633) and Northwestern University. The computational work by J.M.R. and M.J.W. was supported by the National Science Foundation (NSF) Grant No. DMR-2011208, and that by C.W. and S.H. was partially supported by the Department of Energy, Office of Science Basic Energy Sciences, under Grant No. DE-SC0014520, DOE Office of Science. Access to facilities for high-performance computing resources at Northwestern University is acknowledged. J.I.J. acknowledges the support of the Basic Science Research Programs (2020R1F1A1069646 and 2021R1A2C2013625) through the National Research Foundation of Korea (NRF), funded by the Korean government. The authors thank Dr. Daniel G. Chica and Dr. Vladislav Klepov for useful discussions and productive conversations.
ASJC Scopus subject areas
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry
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CSD 2100721: Experimental Crystal Structure Determination
Iyer, A. K. (Contributor), Cho, J. B. (Contributor), Byun, H. R. (Contributor), Waters, M. J. (Contributor), Hao, S. (Contributor), Oxley, B. M. (Contributor), Gopalan, V. (Contributor), Wolverton, C. (Contributor), Rondinelli, J. M. (Contributor), Jang, J. I. (Contributor) & Kanatzidis, M. G. (Contributor), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 2021
DOI: 10.25505/fiz.icsd.cc28hz6z, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc28hz6z&sid=DataCite
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CSD 2100718: Experimental Crystal Structure Determination
Iyer, A. K. (Contributor), Cho, J. B. (Contributor), Byun, H. R. (Contributor), Waters, M. J. (Contributor), Hao, S. (Contributor), Oxley, B. M. (Contributor), Gopalan, V. (Contributor), Wolverton, C. (Contributor), Rondinelli, J. M. (Contributor), Jang, J. I. (Contributor) & Kanatzidis, M. G. (Contributor), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 2021
DOI: 10.25505/fiz.icsd.cc28hz3w, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc28hz3w&sid=DataCite
Dataset
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CSD 2100720: Experimental Crystal Structure Determination
Iyer, A. K. (Contributor), Cho, J. B. (Contributor), Byun, H. R. (Contributor), Waters, M. J. (Contributor), Hao, S. (Contributor), Oxley, B. M. (Contributor), Gopalan, V. (Contributor), Wolverton, C. (Contributor), Rondinelli, J. M. (Contributor), Jang, J. I. (Contributor) & Kanatzidis, M. G. (Contributor), FIZ Karlsruhe - Leibniz Institute for Information Infrastructure, 2021
DOI: 10.25505/fiz.icsd.cc28hz5y, http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.25505/fiz.icsd.cc28hz5y&sid=DataCite
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