Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of ACsP2Se8 (A = K, Rb, Cs)

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

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Abstract

The soluble molecular selenophosphate salts ACsP2Se8 (A = K, Rb, Cs) crystallize in the orthorhombic space group Ccce with a = 14.982(3) Å, b = 24.579(5) Å, and c = 13.065(3) Å for the Cs salt and a = 14.782(3) Å, b = 23.954(5) Å, and c = 13.044(3) Å 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 ACsP2Se8 of 2.12 ± 0.2 eV. Raman spectroscopic studies exhibit active modes of PSe4 and Se-Se in the compound. Solution 31P 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 ACsP2Se8 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, χ(3), for amorphous and crystalline Cs2P2Se8 of 1.8 ± 0.2 × 105 pm2/V2 and 2.4 ± 0.1 × 105 pm2/V2, respectively.

Original languageEnglish
Pages (from-to)2374-2383
Number of pages10
JournalChemistry of Materials
Volume28
Issue number7
DOIs
Publication statusPublished - Apr 26 2016

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Harmonic generation
Conformations
Energy gap
Salts
Phase transitions
Alkali Metals
Alkali metals
Synchrotrons
X ray powder diffraction
Thermoanalysis
Anions
Quenching
Negative ions
Nuclear magnetic resonance
Crystalline materials
Water
selenophosphate

ASJC Scopus subject areas

  • Materials Chemistry
  • Chemical Engineering(all)
  • Chemistry(all)

Cite this

Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of ACsP2Se8 (A = K, Rb, Cs). / Haynes, Alyssa S.; Banerjee, Abhishek; Saouma, Felix O.; Otieno, Calford O.; Jang, Joon I.; Kanatzidis, Mercouri G.

In: Chemistry of Materials, Vol. 28, No. 7, 26.04.2016, p. 2374-2383.

Research output: Contribution to journalArticle

Haynes, Alyssa S. ; Banerjee, Abhishek ; Saouma, Felix O. ; Otieno, Calford O. ; Jang, Joon I. ; Kanatzidis, Mercouri G. / Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of ACsP2Se8 (A = K, Rb, Cs). In: Chemistry of Materials. 2016 ; Vol. 28, No. 7. pp. 2374-2383.
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abstract = "The soluble molecular selenophosphate salts ACsP2Se8 (A = K, Rb, Cs) crystallize in the orthorhombic space group Ccce with a = 14.982(3) {\AA}, b = 24.579(5) {\AA}, and c = 13.065(3) {\AA} for the Cs salt and a = 14.782(3) {\AA}, b = 23.954(5) {\AA}, and c = 13.044(3) {\AA} 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 ACsP2Se8 of 2.12 ± 0.2 eV. Raman spectroscopic studies exhibit active modes of PSe4 and Se-Se in the compound. Solution 31P 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 ACsP2Se8 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, χ(3), for amorphous and crystalline Cs2P2Se8 of 1.8 ± 0.2 × 105 pm2/V2 and 2.4 ± 0.1 × 105 pm2/V2, respectively.",
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T1 - Phase Transition, Conformational Exchange, and Nonlinear Optical Third Harmonic Generation of ACsP2Se8 (A = K, Rb, Cs)

AU - Haynes, Alyssa S.

AU - Banerjee, Abhishek

AU - Saouma, Felix O.

AU - Otieno, Calford O.

AU - Jang, Joon I.

AU - Kanatzidis, Mercouri G

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N2 - The soluble molecular selenophosphate salts ACsP2Se8 (A = K, Rb, Cs) crystallize in the orthorhombic space group Ccce with a = 14.982(3) Å, b = 24.579(5) Å, and c = 13.065(3) Å for the Cs salt and a = 14.782(3) Å, b = 23.954(5) Å, and c = 13.044(3) Å 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 ACsP2Se8 of 2.12 ± 0.2 eV. Raman spectroscopic studies exhibit active modes of PSe4 and Se-Se in the compound. Solution 31P 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 ACsP2Se8 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, χ(3), for amorphous and crystalline Cs2P2Se8 of 1.8 ± 0.2 × 105 pm2/V2 and 2.4 ± 0.1 × 105 pm2/V2, respectively.

AB - The soluble molecular selenophosphate salts ACsP2Se8 (A = K, Rb, Cs) crystallize in the orthorhombic space group Ccce with a = 14.982(3) Å, b = 24.579(5) Å, and c = 13.065(3) Å for the Cs salt and a = 14.782(3) Å, b = 23.954(5) Å, and c = 13.044(3) Å 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 ACsP2Se8 of 2.12 ± 0.2 eV. Raman spectroscopic studies exhibit active modes of PSe4 and Se-Se in the compound. Solution 31P 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 ACsP2Se8 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, χ(3), for amorphous and crystalline Cs2P2Se8 of 1.8 ± 0.2 × 105 pm2/V2 and 2.4 ± 0.1 × 105 pm2/V2, respectively.

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