Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of A CsP ₂ Se ₈ ( A = K, Rb, Cs)

Journal Article · Tue Apr 12 00:00:00 EDT 2016 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b00551· OSTI ID:1352633

Haynes, Alyssa S.; Banerjee, Abhishek; Saouma, Felix O.; Otieno, Calford O.; Jang, Joon I.; Kanatzidis, Mercouri G.

The soluble molecular selenophosphate salts ACsP(2)Se(8) (A = K, Rb, Cs) crystallize in the orthorhombic space group Ccce with a = 14.982(3) A, b = 24.579(5) A, and c = 13.065(3) A for the Cs salt and a = 14.782(3) A, b = 23.954(5) A, and c = 13.044(3) A for the K analogue. ACsP2Se8 is composed of the molecular 6-membered ring, [P2Se8](2-), in the twist conformation charge balanced by alkali metals. The band gaps of these compounds are 2.44 +/- 0.2 eV for Cs2P2Se8, 2.41 +/- 0.2 eV for RbCsP2Se8, and 2.36 +/- 0.2 eV for KCsP2Se8. The amorphous versions of these materials can be made by water quenching the melt and have band gaps for all ACsP(2)Se(8) of 2.12 +/- 0.2 eV. Raman spectroscopic studies exhibit active modes of PSe4 and Se Se in the compound. Solution P-31 NMR studies shed light into the interesting conformational fluxionality of the [P2Se8](2-) anion, including a conformation that has not been previously observed. Thermal analysis reveals ACsP(2)Se(8) exhibits a phase transition, which we investigate by in situ synchrotron powder X-ray diffraction. Third harmonic generation (THG) nonlinear optical measurements determined the THG coefficient, chi(3), for amorphous and crystalline Cs2P2Se8 of 1.8 +/- 0.2 X 105 pm(2)/V-2 and 2.4 +/- 0.1 X 105 pm2/V2, respectively.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States)
• Sponsoring Organization: USDOE Office of Science - Office of Basic Energy Sciences - Materials Sciences and Engineering Division
• DOE Contract Number: AC02-06CH11357
• OSTI ID: 1352633
• Journal Information: Chemistry of Materials, Vol. 28, Issue 7; ISSN 0897-4756
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: English