1 research outputs found
Large Second-Harmonic Generation Responses Achieved by the Dimeric [Ge<sub>2</sub>Se<sub>4</sub>(μ-Se<sub>2</sub>)]<sup>4–</sup> Functional Motif in Polar Polyselenides A<sub>4</sub>Ge<sub>4</sub>Se<sub>12</sub> (A = Rb, Cs)
Two new polar polyselenides
Rb<sub>4</sub>Ge<sub>4</sub>Se<sub>12</sub> (<b>1</b>) and Cs<sub>4</sub>Ge<sub>4</sub>Se<sub>12</sub> (<b>2</b>) with rarely
reported dimeric [Ge<sub>2</sub>Se<sub>4</sub>(μ-Se<sub>2</sub>)]<sup>4–</sup> units
were synthesized. They present large second-harmonic generation (SHG)
intensities of 7.5 and 6.5 times that of the benchmark AgGaS<sub>2</sub> with type I phase-matching behavior, high laser-induced damaged
thresholds, a wide transmission region and congruently melting behavior,
making them excellent candidates for IR nonlinear optical (NLO) applications.
The SHG functional motifs of both compounds are determined to be [Ge<sub>2</sub>Se<sub>4</sub>(μ-Se<sub>2</sub>)]<sup>4–</sup> unit by time-dependent density functional theory calculation, which
further reveals that charge transfers from the lone pairs of terminal
Se atoms to the five σ* orbitals of five-membered ring Ge<sub>2</sub>Se<sub>3</sub> have a predominant contribution to the total
SHG effect