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M4Mg4(P2O7)3 (M = K, Rb): Structural Engineering of Pyrophosphates for Nonlinear Optical Applications
Chemistry of Materials ( IF 7.2 ) Pub Date : 2017-02-13 00:00:00 , DOI: 10.1021/acs.chemmater.7b00167 Hongwei Yu 1 , Joshua Young 2 , Hongping Wu 1, 3 , Weiguo Zhang 1 , James M. Rondinelli 2 , P. Shiv Halasyamani 1
Chemistry of Materials ( IF 7.2 ) Pub Date : 2017-02-13 00:00:00 , DOI: 10.1021/acs.chemmater.7b00167 Hongwei Yu 1 , Joshua Young 2 , Hongping Wu 1, 3 , Weiguo Zhang 1 , James M. Rondinelli 2 , P. Shiv Halasyamani 1
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On the basis of their short ultraviolet (UV) absorption edges, phosphates are ideal candidates for deep-UV nonlinear optical (NLO) applications. However, their often-weak second-harmonic generating (SHG) responses reduce their NLO applications. It has been demonstrated that the SHG response in polyphosphates or orthophosphates could be enhanced by highly polymerized P–O groups or aligned nonbonding O-2p orbitals of isolated PO4 units. Herein, we report on the design and synthesis of two pyrophosphates, K4Mg4(P2O7)3 and Rb4Mg4(P2O7)3, with potential NLO applications. Both materials exhibit relatively large SHG responses with 1064 nm radiation, 1.3× and 1.4× KH2PO4 (KDP) for K4Mg4(P2O7)3 and Rb4Mg4(P2O7)3, respectively. In addition, absorption edges below 200 nm were observed for both materials. For K4Mg4(P2O7)3, single crystal vacuum-UV transmission measurements revealed an absorption edge of 170 nm. First-principles electronic structure calculations identify that the NLO responses arise from the presence of the corner-connected [Mg4P6O21] double layers. We also investigated these compounds using hybrid density functionals, which are found to produce much better agreement with the experimental optical results. Finally, we detail the structural distortions giving rise to the NLO responses. Our results indicate that phosphates with low polymerized P–O groups, such as pyrophosphates, may exhibit large SHG responses if their structures are properly designed.
中文翻译：
M 4 Mg 4（P 2 O 7）3（M = K，Rb）：用于非线性光学应用的焦磷酸盐的结构工程
基于其短的紫外线（UV）吸收边缘，磷酸盐是深紫外线非线性光学（NLO）应用的理想候选材料。但是，它们通常较弱的二次谐波产生（SHG）响应会减少其NLO应用。已经证明，高度聚合的P–O基团或孤立的PO 4单元的对齐的非键合O-2p轨道可以增强多磷酸盐或正磷酸盐中的SHG反应。在此，我们报告两种焦磷酸盐K 4 Mg 4（P 2 O 7）3和Rb 4 Mg 4（P 2 O 7）3的设计与合成。，具有潜在的NLO应用程序。两种材料在1064 nm辐射下均表现出相对较大的SHG响应，分别对于K 4 Mg 4（P 2 O 7）3和Rb 4 Mg 4（P 2 O 7）3分别为1.3×和1.4×KH 2 PO 4（KDP）。。另外，两种材料均观察到低于200 nm的吸收边缘。对于K 4 Mg 4（P 2 O 7）3，单晶真空-UV透射测量显示出170nm的吸收边缘。第一性原理电子结构计算确定NLO响应是由角连接的[Mg 4 P 6 O 21 ]双层的存在引起的。我们还使用混合密度泛函对这些化合物进行了研究，发现它们与实验光学结果具有更好的一致性。最后，我们详细介绍了引起NLO响应的结构扭曲。我们的结果表明，如果结构设计合理，则具有低聚合P–O基团的磷酸盐（例如焦磷酸盐）可能表现出较大的SHG响应。
更新日期：2017-02-13
中文翻译：
M 4 Mg 4（P 2 O 7）3（M = K，Rb）：用于非线性光学应用的焦磷酸盐的结构工程
基于其短的紫外线（UV）吸收边缘，磷酸盐是深紫外线非线性光学（NLO）应用的理想候选材料。但是，它们通常较弱的二次谐波产生（SHG）响应会减少其NLO应用。已经证明，高度聚合的P–O基团或孤立的PO 4单元的对齐的非键合O-2p轨道可以增强多磷酸盐或正磷酸盐中的SHG反应。在此，我们报告两种焦磷酸盐K 4 Mg 4（P 2 O 7）3和Rb 4 Mg 4（P 2 O 7）3的设计与合成。，具有潜在的NLO应用程序。两种材料在1064 nm辐射下均表现出相对较大的SHG响应，分别对于K 4 Mg 4（P 2 O 7）3和Rb 4 Mg 4（P 2 O 7）3分别为1.3×和1.4×KH 2 PO 4（KDP）。。另外，两种材料均观察到低于200 nm的吸收边缘。对于K 4 Mg 4（P 2 O 7）3，单晶真空-UV透射测量显示出170nm的吸收边缘。第一性原理电子结构计算确定NLO响应是由角连接的[Mg 4 P 6 O 21 ]双层的存在引起的。我们还使用混合密度泛函对这些化合物进行了研究，发现它们与实验光学结果具有更好的一致性。最后，我们详细介绍了引起NLO响应的结构扭曲。我们的结果表明，如果结构设计合理，则具有低聚合P–O基团的磷酸盐（例如焦磷酸盐）可能表现出较大的SHG响应。
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