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本文利用偏振拉曼光谱和第一性原理, 对磷酸二氢铵(NH4H2PO4, ADP)和不同氘含量磷酸二氢铵DADP晶体的晶格振动模式进行了研究. 实验测得了不同几何配置、2004000 cm-1范围的偏振拉曼光谱, 分析在不同氘含量条件下921 cm-1和3000 cm-1附近拉曼峰的变化. 在ADP晶体中, 基于基本结构单元NH4+ 和H2PO4-基团的振动模, 用第一性原理进行了数值模拟, 进一步明确拉曼峰与晶体中原子振动的对应关系; 通过洛伦兹拟合不同氘含量DADP晶体的拉曼光谱中20002600 cm-1处各峰的变化讨论了DADP 晶体的氘化过程, 结果表明氘化顺序是先NH4+ 基团后H2PO4-基团, 研究结果为今后此类材料的生长和性能优化奠定了基础.
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关键词:
- NH4H2PO4和ND4D2PO4 /
- 拉曼光谱 /
- 第一性原理 /
- 振动模式
In this paper, the lattice vibration modes of ammonium dihydrogen phosphate NH4H2PO4 (ADP) and its deuterated analog DADP are studied by using polarized Raman spectra and the first-principles calculation in the framework of the density functional theory. The vibration modes of ADP crystal, in which the basic structural units are the NH4+ and H2 PO4-groups, have been simulated by using a plane-wave pseudo potential method. Result shows that the peaks of 921 and near 3400 cm-1 are assigned as the vibrational H2 PO4-and NH4+ groups, respectively. In order to investigate the deuteration process, the polarized Raman spectra are obtained in different polarization configurations and recorded in the range of 200-4000 cm-1, so that we can study the variation of Raman peaks at 921 and 26003400 cm-1. For example, in the scattering geometryX(YY)X , with increasing degree of deuterated, the peak of 921 cm-1 red shifts and decreases in intensity, while the peaks ranging from 2600 to 3000 cm-1 decrease in intensity. Moreover, a new broadened line appears in the range of 20002600 cm-1, and the intensity of the new line increases with the degree of deuterated, but no change occurs in the peak position. With Lorentz analysis, it can be inferred that the deuterated of NH4+ group is prior to that of H2 PO4-group. We also study the spectra for other Raman scattering geometry of these crystals, and the result shows that the site symmetries of NH4+ (ND4+) and H2 PO4-(D2 PO4-) groups are determined to be C2, which means that the site symmetry of the two groups in crystals have no change during the deuteration process. These results will be a foundaton for optimizing the growth and property of this kind of material.[1] Dvořk V 1963 physica. Status. Solidi. 3 2235
[2] Rez I S 1968 Phys. Usp. 10 759
[3] Kaminskii A A, Dolbinina V V, Rhee H, Eichler H J, Ueda K, Takaichi K, Shirakawa A, Tokurakawa M, Dong J, Jaque D 2008 Laser Phys. Lett. 5 532
[4] Ji S, Wang F, Xu M, Zhu L, Xu X, Wang Z, Sun X 2013 Opt. Lett. 38 1679
[5] Zhou H L, Zhang Q H, Wang B, Xu X G, Wang Z P, Sun X, Zhang F, Zhang L S, Liu B A, Chai X X 2015 Chin. Phys. B 24 044206
[6] Liu B A, Zhou H L, Zhang Q H, Xu M X, Ji S H, Zhu L L, Zhang L S, Liu F F, Sun X, Xu X G 2013 Chin. Phys. Lett. 30 067804
[7] Kasahara M, Tokunaga M, Tatsuzaki I 1986 J. Phys. Soc. Jpn. 55 367
[8] Fukami T, Akahoshi S, Hukuda K, Yagi T 1987 J. Phys. Soc. Jpn. 56 4388
[9] Hadrich A, Lautie A, Mhiri T 2000 J. Raman. Spectrosc. 31 587
[10] Gorelik V S, Kaminskii A A, Melnik N N, Melnik N N, Sverbil P P, Voinov Y P, Zavaritskaya T N, and Zlobina L I 2008 J. Russ. Laser Res. 29 357
[11] Prs N, Boukhris A, Souhassou M, Souhassou M, Gavoille G, Lecomte C 1999 Acta. crystallogr. A 55 1038
[12] Segall M D, Lindan P J, Probert, M A, Pickard C J, Hasnip P J, Clark S J, Payne M C, Probert M J 2002 J. Phys. Condens. Mat. 14 2717
[13] Wu Z, Cohen R E 2006 Phys. Rev. B 73 235116
[14] Hamann D R, Schlter M, Chiang C 1979 Phys. Rev. Lett. 43 1494
[15] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[16] Baroni S, De Gironcoli S, Dal Corso A, Giannozzi P 2001 Rev. Mod. Phys. 73 515
[17] Piltz R O, McMahon M I, Nelmes R J 1991 Zeitschrift fr Kristallographie-Crystalline Materials 195 241
[18] Loudon R 1964 Adv.Phys. 13 423
[19] Lu G W, Sun X 2002 Cryst. Res. Technol 37 93
[20] Kasahara M, Tokunaga M, Tatsuzaki I 1986 J. Phys. Soc. Jpn. 55 367
[21] Huser T, Hollars C W, Siekhaus W J, De Yoreo J J, Suratwala T I, Land, T A 2004 Appl. Spectrosc. 58 349
[22] Pends A M, Blanco M A, Francisco E 2006 J. Chem. Phys. 125 184112
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[1] Dvořk V 1963 physica. Status. Solidi. 3 2235
[2] Rez I S 1968 Phys. Usp. 10 759
[3] Kaminskii A A, Dolbinina V V, Rhee H, Eichler H J, Ueda K, Takaichi K, Shirakawa A, Tokurakawa M, Dong J, Jaque D 2008 Laser Phys. Lett. 5 532
[4] Ji S, Wang F, Xu M, Zhu L, Xu X, Wang Z, Sun X 2013 Opt. Lett. 38 1679
[5] Zhou H L, Zhang Q H, Wang B, Xu X G, Wang Z P, Sun X, Zhang F, Zhang L S, Liu B A, Chai X X 2015 Chin. Phys. B 24 044206
[6] Liu B A, Zhou H L, Zhang Q H, Xu M X, Ji S H, Zhu L L, Zhang L S, Liu F F, Sun X, Xu X G 2013 Chin. Phys. Lett. 30 067804
[7] Kasahara M, Tokunaga M, Tatsuzaki I 1986 J. Phys. Soc. Jpn. 55 367
[8] Fukami T, Akahoshi S, Hukuda K, Yagi T 1987 J. Phys. Soc. Jpn. 56 4388
[9] Hadrich A, Lautie A, Mhiri T 2000 J. Raman. Spectrosc. 31 587
[10] Gorelik V S, Kaminskii A A, Melnik N N, Melnik N N, Sverbil P P, Voinov Y P, Zavaritskaya T N, and Zlobina L I 2008 J. Russ. Laser Res. 29 357
[11] Prs N, Boukhris A, Souhassou M, Souhassou M, Gavoille G, Lecomte C 1999 Acta. crystallogr. A 55 1038
[12] Segall M D, Lindan P J, Probert, M A, Pickard C J, Hasnip P J, Clark S J, Payne M C, Probert M J 2002 J. Phys. Condens. Mat. 14 2717
[13] Wu Z, Cohen R E 2006 Phys. Rev. B 73 235116
[14] Hamann D R, Schlter M, Chiang C 1979 Phys. Rev. Lett. 43 1494
[15] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
[16] Baroni S, De Gironcoli S, Dal Corso A, Giannozzi P 2001 Rev. Mod. Phys. 73 515
[17] Piltz R O, McMahon M I, Nelmes R J 1991 Zeitschrift fr Kristallographie-Crystalline Materials 195 241
[18] Loudon R 1964 Adv.Phys. 13 423
[19] Lu G W, Sun X 2002 Cryst. Res. Technol 37 93
[20] Kasahara M, Tokunaga M, Tatsuzaki I 1986 J. Phys. Soc. Jpn. 55 367
[21] Huser T, Hollars C W, Siekhaus W J, De Yoreo J J, Suratwala T I, Land, T A 2004 Appl. Spectrosc. 58 349
[22] Pends A M, Blanco M A, Francisco E 2006 J. Chem. Phys. 125 184112
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