A$_2$P$_2$S$_6$ (A = Ba and Pb): a good platform to study the polymorph effect and lone pair effect to form an acentric structure
Ji, Bingheng Sarkar, Arka Wu, Kui Swindle, Andrew L. Wang, Jian
Ji, Bingheng
Sarkar, Arka
Wu, Kui
Swindle, Andrew L.
Wang, Jian
Citations
Altmetric:
Other Names
Location
Time Period
Advisors
Original Date
Digitization Date
Issue Date
2022-05-14
Type
Article
Genre
Keywords
Barium compounds,Crystal structure,Differential scanning calorimetry,Electronic structure,Gallium compounds,Harmonic generation,Laser damage,Lead compounds,Nonlinear optics,Optical properties,Phase matching,Silver compounds,Single crystals,Centrosymmetric,Harmonics generation,Highest temperature,I-phase,Laser damage threshold,Lone-pair effects,Matching materials,Phase-matching,Second harmonics
Subjects (LCSH)
Citation
Ji, B., Sarkar, A., Wu, K., Swindle, A., & Wang, J. (2022 ). A2P2S6 (A = Ba and Pb): a good platform to study the polymorph effect and lone pair effect to form an acentric structure. Dalton Transactions, 51(11). https://doi.org/http://dx.doi.org/10.1039/D1DT04317J
Abstract
Three ternary thiophosphates α-Ba$_2$P$_2$S$_6$, β-Ba$_2$P$_2$S$_6$, and Pb$_2$P$_2$S$_6$ were synthesized via a high temperature salt flux method or an I2 transport reaction. β-Ba$_2$P$_2$S$_6$ and Pb$_2$P$_2$S$_6$ were previously structurally characterized without investigating their optical properties. α-Ba$_2$P$_2$S$_6$ was discovered for the first time, and it is isostructural to Pb$_2$P$_2$S$_6$ and crystallizes in the acentric space group Pn (no. 7). β-Ba$_2$P$_2$S$_6$ crystallizes in the centrosymmetric space group P21/n (no. 14). There is a high structural similarity between α-Ba$_2$P$_2$S$_6$, β-Ba$_2$P$_2$S$_6$, and Pb$_2$P$_2$S$_6$ including close unit cell parameters and identical [P2S6] motifs. The structural relationships between α-Ba$_2$P$_2$S$_6$ and β-Ba$_2$P$_2$S$_6$, and β-Ba$_2$P$_2$S$_6$ and Pb$_2$P$_2$S$_6$ were elucidated by single crystal X-ray diffraction, differential scanning calorimetry (DSC), electronic structure calculations, and nonlinear optical property measurements. There are no phase transitions detected between α-Ba$_2$P$_2$S$_6$ and β-Ba$_2$P$_2$S$_6$. From centrosymmetric β-Ba$_2$P$_2$S$_6$ to acentric Pb$_2$P$_2$S$_6$, the chemical characteristics of Pb, such as stereoactive lone pairs, play a key role in the structural difference. Pb$_2$P$_2$S$_6$ is uncovered as a type-I phase-matching material with a moderate second harmonic generation (SHG) response of 1.4 × AgGaS$_2$ and a high laser damage threshold (LDT) of 2.5 × AgGaS$_2$. α-Ba$_2$P$_2$S$_6$ is not a type-I phase-matching material with a moderate second harmonic generation response (1.7 × AgGaS$_2$, a sample of 225 μm particle size) and a high laser damage threshold (5.5 × AgGaS$_2$).
Table of Contents
Description
Click on the DOI to access this article (may not be free).
Publisher
The Royal Society of Chemistry
Journal
Book Title
Series
Dalton Transactions;Volume 51, Issue 11
Digital Collection
Finding Aid URL
Use and Reproduction
Archival Collection
PubMed ID
DOI
ISSN
1477-9226