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L-arginine phosphate monohydrate (LAP) crystal is an excellent nonlinear optical material, its effective nonlinear optical coefficient is about 2−3.5 times that of potassium dideuterium phosphate (KDP) crystal, and its conversion efficiency can achieve up to 90%. The deuterated crystal of LAP has a very high laser damage threshold. Thus, once it was considered as a preferred material to replace KDP crystal for laser inertial confinement fusion and other fields. In addition, the LAP crystal has a much higher stimulated Brillouin scattering (SBS) reflectivity than quartz crystal and also has a lower SBS threshold. Moreover, it exhibits a special reversible phase-change in the variable temperature process, and shows an ultra-long spin-lattice relaxation time at solid-state NMR. In a word, the LAP crystal has shown its uniqueness under the action of energy such as light, heat and magnetic field. However, for these special phenomena, there is no reasonable explanation. Phosphate arginine is responsible for the biological energy storage and transfer in invertebrates as an important phosphorus source, which has a similar chemical composition to that of LAP crystal. The special electrostatic or hydrogen bonding interaction between guanidine and phosphate plays an important role in protein molecule interaction and their biochemical functions. Moreover, the conformational transitions of L-arginine molecule in phosphoric acid solution at different energies have been reported, and the fluorescence emission of L-arginine molecule aggregates can be changed by the interaction between phosphoate and guanidine group. The interaction between phosphoate and guanidine group in crystal structure is also studied as a model of biomolecular interaction. In order to further study the mechanism of interaction between phosphoate and guanidine group and the crystal macroscopic properties, phosphate bis-guanidinoacetate (PBGA) crystal containing the similar phosphoate and guanidine groups has been synthesized and reported. In this paper, the geometry parameters, band structure, electronic density of states, and optical properties of PBGA crystal are investigated by first-principles based the density functional theory. The energy gap of PBGA crystal is 4.77 eV, much smaller than 5.96 eV of KDP crystal. Therefore, the photon transition becomes easier and the corresponding photon absorption is relatively large in PBGA crystal. The top states of crystal valence band are mainly composed of the N-2p of guanidine and the O-2p of carboxyl and phosphate groups. There exists the electron interaction among guanidine, carboxyl and phosphate groups. The optical properties of PBGA crystal are similar in the [100] and [010] orientation, whose linear optical properties are better than those of [001] when the incident photon energy is less than 10 eV. The strong energy loss peak at 9.46 eV in the [001] orientation is due to the electronic transition of N-2p on guanidine group in the valence band, and its distribution is narrow. Thus the optical properties of [001] orientation are limited. The present research establishes a good foundation for further understanding and studying the intergroup interactions and optical properties in PBGA crystal.
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Keywords:
- phosphate bis-guanidinoacetate /
- first principles /
- electronic structure /
- optical properties
[1] 王镜岩, 朱圣庚, 徐长法 2002 生物化学 (第三版下册) (北京: 高等教育出版社) 第41页
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图 1 PBGA晶体的(a)分子构型和(b)沿a轴方向的投影图
Figure 1. (a) Molecular configuration and (b) projection viewed along a-axis of PBGA crystal
图 2 PBGA晶体(a)原始模型与(b)优化后模型
Figure 2. (a) Original and (b) optimized model of PBGA crystal
图 3 PBGA晶体的分态密度
Figure 3. Partial density of states of PBGA crystal
图 4 PBGA晶体中(a)氧和(b)氮的p轨道分态密度
Figure 4. The p-orbital partial density of states of (a) oxygen and (b) nitrogen in PBGA crystal
图 5 PBGA晶体的介电函数虚部与能量关系
Figure 5. Relationship between energy and imaginary part of dielectric function of PBGA crystal
图 6 PBGA晶体的(a)折射率和(b)吸收系数
Figure 6. (a) Refractive index and (b) absorption coefficient of PBGA crystal
图 7 PBGA晶体的(a)反射率与(b)能量损失函数
Figure 7. (a) Reflectivity and (b) loss function of PBGA crystal
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[1] 王镜岩, 朱圣庚, 徐长法 2002 生物化学 (第三版下册) (北京: 高等教育出版社) 第41页
Wang J Y, Zhu S G, Xu C F 2002 Biochemistry (3rd Ed.) Vol. 2 (Beijing: Higher Education Press) p41 (in Chinese)
[2] Bailey D M, Peck L S, Bock C, Portner H 2003 Physiol. Biochem. Zool. 76 622
Google Scholar
[3] Senior A E, Nadanaciva S, Weber J 2002 Biochem. Biophys. Acta 1553 188
Google Scholar
[4] Xian L, Liu S, Ma Y, Lu G 2007 Spectrochim. Acta Part A 67 368
Google Scholar
[5] Mandell D J, Chorny I, Groban E S, Wong S E, Levine E, Rapp C S, Jacobson M P 2007 J. Am. Chem. Soc. 129 820
Google Scholar
[6] Tang M, Waring A J, Lehrer R I, Hong M 2008 Angew. Chem. Int. Ed. 47 3202
Google Scholar
[7] Cotton F A, Day V W, Hazen E E, Larsen S 1973 J. Am. Chem. Soc. 95 4834
Google Scholar
[8] 许东, 蒋民华, 谭忠恪 1983 化学学报 41 570
Xu D, Jiang M H, Tan Z K 1983 Acta Chim. Sin. 41 570
[9] Eimerl D, Velsko S, Davis L, Wang F, Loiacono G, Kennedy G 1989 IEEE J. Quantum Electron. 25 179
Google Scholar
[10] Eimerl D 1985 LLNL Report UCID 20565 92
[11] Yoshimura M, Mori Y, Sasaki T, Yoshida H, Nakatsuka M 1998 J. Opt. Soc. Am. 15 446
Google Scholar
[12] 孙贵花 2011 博士学位论文 (济南: 山东大学)
Sun G H 2011 Ph. D. Dissertation (Jinan: Shandong University) (in Chinese)
[13] Wang L N, Zhang G H, Wang X Q, Wang L, Liu X T, Jin L T, Xu D 2012 J. Mol. Strct. 1026 71
Google Scholar
[14] Liu X T, Wang L, Wang L N, Zhang G H, Wang X Q, Xu D 2014 Int. J. Mater. Sci. 4 39
Google Scholar
[15] 王磊 2014 博士学位论文 (济南: 山东大学)
Wang L 2014 Ph. D. Dissertation (Jinan: Shandong University) (in Chinese)
[16] Segall M D, Lindan P J D, Probert M J, Pickard C J, Hasnip P J, Clark S J, Payne M C 2002 J. Phys. Condens. Mater. 14 2717
Google Scholar
[17] Perdew J P, Wang Y 1992 Phys. Rev. B 45 13244
Google Scholar
[18] Vanderbilt D 1990 Phys. Rev. B 41 7892
Google Scholar
[19] 段满益, 徐明, 周海平, 陈青云, 胡志刚, 董成军 2008 物理学报 57 6520
Google Scholar
Duan M Y, Xu M, Zhou H P, Chen Q Y, Hu Z G, Dong C J 2008 Acta Phys. Sin. 57 6520
Google Scholar
[20] Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188
Google Scholar
[21] 沈学础 1992 半导体光学性质 (北京: 科学出版社) 第24页
Shen X C 1992 Optical Property of Semiconductor (Beijing: Science Press) p24 (in Chinese)
[22] 徐大庆, 赵子涵, 李培咸, 王超, 张岩, 刘树林, 童军 2018 物理学报 67 087501
Google Scholar
Xu D Q, Zhao Z H, Li P X, Wang C, Zhang Y, Liu S L, Tong J 2018 Acta Phys. Sin. 67 087501
Google Scholar
[23] Zhang Q, Chen F, Kioussis N, Demos S G, Radousky H B 2001 Phys. Rev. B 65 024108
Google Scholar
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