TY - JOUR
T1 - Flexible polar nanowires of Cs 5BiP 4Se 12 from weak interactions between coordination complexes
T2 - Strong nonlinear optical second harmonic generation
AU - Chung, In
AU - Song, Jung Hwan
AU - Jang, Joon I.
AU - Freeman, Arthur J.
AU - Ketterson, John B.
AU - Kanatzidis, Mercouri G.
PY - 2009/2/25
Y1 - 2009/2/25
N2 - The Cs 5BiP 4Se 12 salt grows naturally as nanowires that crystallize in the polar space group PmC2 1, with a = 7.5357(2) Å, b = 13.7783(6) Å, c = 28.0807(8) Å, and Z = 4 at 293(2) K. The compound features octahedral [Bi(P 2Se 6) 2] 5-coordination complexes that stack via weak intermolecular Se⋯Se interactions to form long, flexible fibers and nanowires. The Cs 5BiP 4Se 12 fibers are transparent in the near-and mid-IR ranges and were found to exhibit a nonlinear optical second harmonic generation response at 1 μm that is approximately twice that of the benchmark material AgGaSe 2. The material has a nearly direct band gap of 1.85 eV and melts congruently at 590 °C. Ab initio electronic structure calculations performed with the full-potential linearized augmented plane wave (FLAPW) method show that the band gap increases from its local density approximation (LDA) spin-orbit coupling value of 1.15 eV to the higher value of 2.0 eV when the screened-exchange LDA method is invoked and explain how the long nanowire nature of Cs 5BiP 4Se 12 emerges.
AB - The Cs 5BiP 4Se 12 salt grows naturally as nanowires that crystallize in the polar space group PmC2 1, with a = 7.5357(2) Å, b = 13.7783(6) Å, c = 28.0807(8) Å, and Z = 4 at 293(2) K. The compound features octahedral [Bi(P 2Se 6) 2] 5-coordination complexes that stack via weak intermolecular Se⋯Se interactions to form long, flexible fibers and nanowires. The Cs 5BiP 4Se 12 fibers are transparent in the near-and mid-IR ranges and were found to exhibit a nonlinear optical second harmonic generation response at 1 μm that is approximately twice that of the benchmark material AgGaSe 2. The material has a nearly direct band gap of 1.85 eV and melts congruently at 590 °C. Ab initio electronic structure calculations performed with the full-potential linearized augmented plane wave (FLAPW) method show that the band gap increases from its local density approximation (LDA) spin-orbit coupling value of 1.15 eV to the higher value of 2.0 eV when the screened-exchange LDA method is invoked and explain how the long nanowire nature of Cs 5BiP 4Se 12 emerges.
UR - http://www.scopus.com/inward/record.url?scp=67849090917&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=67849090917&partnerID=8YFLogxK
U2 - 10.1021/ja808242g
DO - 10.1021/ja808242g
M3 - Article
C2 - 19183006
AN - SCOPUS:67849090917
VL - 131
SP - 2647
EP - 2656
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 7
ER -