Citation: WANG Wen-Qing, NG Yan, SHEN Xin-Chun, ZHANG Yu-Feng. Experimental Test of“Parity-Time Asymmetry”in Electron Spin-Flip Raman Scattering of the N⁺H…O Hydrogen Bond in Chiral Alanine Crystals[J]. Acta Physico-Chimica Sinica, ;2013, 29(03): 473-478. doi: 10.3866/PKU.WHXB201212273 shu

Experimental Test of“Parity-Time Asymmetry”in Electron Spin-Flip Raman Scattering of the N⁺H…O Hydrogen Bond in Chiral Alanine Crystals

1.
1 Beijing National Laboratory for Molecular Sciences, Department of Applied Chemistry, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China;
2 School of Materials Science & Engineering, Beijing Institute of Fashion Technology, Beijing 100029, P. R. China

Received Date: 13 November 2012
Available Online: 27 December 2012
Fund Project: 国家自然科学基金(21002006, 20452002) (21002006, 20452002)国家科技部基础研究重大项目(2004-973-36)资助 (2004-973-36)

Spontaneous symmetry breaking of the N⁺H…O bond in chiral alanine crystals around 270 K was detected in situ by Raman vibrational scattering with b(cc)b geometry. An electron spin-flip transition of the N⁺H…O mode in D-/L-alanine was observed by the scattering of light with left/right orientation and its spin projection antiparallel to the direction of propagation. It is an internal magnetic field originated from the spin-orbit interaction. An obvious Raman wavenumber shift with opposite in sign and roughly one third of the asymmetry (A) of the scattered photon between D- and L-alanine crystals was observed. This shift was not seen in polycrystalline powder measurements because spin is an axial vector. An electron spin-flip transition of the methyne (C_α－H) mode around 260 K was shown to be approximative coincidence by examining the temperature-dependent relative intensity of asymmetric Raman scattering with c(aa)c geometry. This article provides evidence for the true chirality and parity-time (PT) asymmetry in molecular clusters of D- and L-alanine crystals.
- Parity-time asymmetry,
- Spontaneous symmetry breaking,
- Asymmetric Raman scattering,
- Polar N⁺H…O bond,
- Methyne,
- Electron spin-flip transition,
- True chirality,
- D- and L-alanine crystals
1. [1]
  
  (1) Bonner,W. A. Chirality 2000, 12, 114.
2. [2]
  (2) Fisun, O. I.; Savin, A. V. BioSystems 1992, 27, 129. doi: 10.1016/0303-2647(92)90068-A
3. [3]
  (3) Lee, T. D.; Yang, C. N. Physical Review 1956, 104, 254.doi: 10.1103/PhysRev.104.254
4. [4]
  (4) Friedberg, R.; Lee, T. D. Annals of Physics 2009, 324, 2196.doi: 10.1016/j.aop.2009.05.009
5. [5]
  (5) Mason, S. F. Molecular Optical Activity and the ChiralDdiscriminations; Cambridge University Press: Cambridge,1982.
6. [6]
  (6) Barron, L. D.; Buckingham, A. D. Accounts Chem. Res. 2001,34, 781 doi: 10.1021/ar0100576
7. [7]
  (7) Ray, K.; Ananthavel, S. P.;Waldeck, D. H.; Naaman, R. Science1999, 283, 814. doi: 10.1126/science.283.5403.814
8. [8]
  (8) Popp, J.; Schmitt, M. J. Raman Spectrosc. 2004, 35, 429.
9. [9]
  (9) Robert, J. B.; Barra, A. L. Chirality 2001, 13, 699.
10. [10]
  (10) Simpson, H. J.; Marsh, R. E. Acta Cryst. 1966, 20, 550. doi: 10.1107/S0365110X66001221
11. [11]
  (11) Destro, R.; Marsh, R. E. J. Phys. Chem. 1988, 92, 966. doi: 10.1021/j100315a022
12. [12]
  (12) Cronin, J. R.; Pizzarello, S. Science 1997, 275, 951. doi: 10.1126/science.275.5302.951
13. [13]
  (13) Gledhill, M. Analyst 2001, 126, 1359. doi: 10.1039/b101268l
14. [14]
  (14) Wang,W. Q.; ng, Y.; Liang, Z.; Sun, F. L.; Shi, D. X.; Gao,H. J. Surface Science 2002, 512, L379.
15. [15]
  (15) Guo, H. M.; Liu, H.W.;Wang, Y. L.; Gao, H. J.; ng, Y.;Jiang, H. Y.;Wang,W. Q. Surface Science 2004, 552, 70.doi: 10.1016/j.susc.2003.12.049
16. [16]
  (16) Wang, C. H.; Storms, R. D. J. Chem. Phys. 1971, 55, 5110.doi: 10.1063/1.1676579
17. [17]
  (17) Razzetti, C.; Ardoino, M.; Zanotti, L.; Zha, M.; Paorici, C.Cryst. Res. Technol. 2002, 37, 456. doi: 10.1002/1521-4079(200205)37:5<456::AID-CRAT456>3.0.CO;2-M
18. [18]
  (18) Wilson, C. C.; Myles, D.; Ghosh, M.; Johnson, L. N.;Wang,W.Q. New J. Chem. 2005, 29, 1318. doi: 10.1039/b419295h
19. [19]
  (19) Wang,W. Q.; ng, Y.; Yao, N. Acta Phys. -Chim. Sin. 2005,21, 774. [王文清, 龚, 姚楠. 物理化学学报, 2005, 21,774.] doi: 10.3866/PKU.WHXB20050715
20. [20]
  (20) Adamowicz, R.; Fishman, E. Spectrochimica Acta A 1972, 28,889. doi: 10.1016/0584-8539(72)80060-6
21. [21]
  (21) Migliori, A.; Maxton, P. M.; Clogston, A. M.; Zirngiebl, L. E.M. Phys. Rev. B 1988, 38, 13464. doi: 10.1103/PhysRevB.38.13464
22. [22]
  (22) Vik, A. F.; Yuzyuk, Y. I.; Barthes, M.; Sauvajol, J. L. J. RamanSpectrosc. 2005, 36, 749.
23. [23]
  (23) Murli, C.; Thomas, S.; Venkateswaran, S.; Sharma, S. M.Physics B 2005, 364, 233. doi: 10.1016/j.physb.2005.04.020
24. [24]
  (24) Barthes, M.; Bordallo, H. N.; Denoyer, F.; Lorenzo, J. E.;Zaccaro, J.; Robert, A.; Zontone, F. Eur. Phys. J. B 2004, 37,375.
25. [25]
  (25) Forss, S. A. J. Raman Spec. 1982, 12, 266. doi: 10.1002/jrs.v12:3
26. [26]
  (26) Yi, F. The Phase Transformation of Amino Acid Crystals,Investigation of Phase Transition Mechanism in D- and LalanineSingle Crystals. MS Dissertation, Peking University,Beijing, 1999. [易芳. 氨基酸单晶的相变机制研究[D].北京: 北京大学, 1999.]
27. [27]
  (27) ng,Y. Origin of Homochirality in Biomolecules: TemperatureinducedPhase Transitions in D-/L-alanine Single Crystals. Ph.D. Dissertation, Peking University, Beijing, 2006. [龚.生物分子手性起源——D-/L-丙氨酸晶体变温相变研究[D].北京: 北京大学, 2006.]
28. [28]
  (28) Byler, D. M.; Susi, H. Spectrochimica Acta 1979, 35A, 1365.
29. [29]
  (29) Wang,W. Q.; Min,W.; ng, Y. Acta Phys. -Chim. Sin. 2005,21, 1186. [王文清, 闵玮, 龚. 物理化学学报, 2005, 21,1186.] doi: 10.3866/PKU.WHXB20051026
1. [1]
  Ke QIAO , Yanlin LI , Shengli HUANG , Guoyu YANG . Advancements in asymmetric catalysis employing chiral iridium (ruthenium) complexes. Chinese Journal of Inorganic Chemistry, 2024, 40(11): 2091-2104. doi: 10.11862/CJIC.20240265
2. [2]
  Qianwen Han , Tenglong Zhu , Qiuqiu Lü , Mahong Yu , Qin Zhong . 氢电极支撑可逆固体氧化物电池性能及电化学不对称性优化. Acta Physico-Chimica Sinica, 2025, 41(1): 2309037-. doi: 10.3866/PKU.WHXB202309037
3. [3]
  Hong Lu , Yidie Zhai , Xingxing Cheng , Yujia Gao , Qing Wei , Hao Wei . Advancements and Expansions in the Proline-Catalyzed Asymmetric Aldol Reaction. University Chemistry, 2024, 39(5): 154-162. doi: 10.3866/PKU.DXHX202310074
4. [4]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
5. [5]
  Dongheng WANG , Si LI , Shuangquan ZANG . Construction of chiral alkynyl silver chains and modulation of chiral optical properties. Chinese Journal of Inorganic Chemistry, 2025, 41(1): 131-140. doi: 10.11862/CJIC.20240379
6. [6]
  Jin Tong , Shuyan Yu . Crystal Engineering for Supramolecular Chirality. University Chemistry, 2024, 39(3): 86-93. doi: 10.3866/PKU.DXHX202308113
7. [7]
  Renxiao Liang , Zhe Zhong , Zhangling Jin , Lijuan Shi , Yixia Jia . A Palladium/Chiral Phosphoric Acid Relay Catalysis for the One-Pot Three-Step Synthesis of Chiral Tetrahydroquinoline. University Chemistry, 2024, 39(5): 209-217. doi: 10.3866/PKU.DXHX202311024
8. [8]
  Haiying Wang , Andrew C.-H. Sue . How to Visually Identify Homochiral Crystals. University Chemistry, 2024, 39(3): 78-85. doi: 10.3866/PKU.DXHX202309004
9. [9]
  Keying Qu , Jie Li , Ziqiu Lai , Kai Chen . Unveiling the Mystery of Chirality from Tartaric Acid. University Chemistry, 2024, 39(9): 369-378. doi: 10.12461/PKU.DXHX202310091
10. [10]
  Xilin Zhao , Xingyu Tu , Zongxuan Li , Rui Dong , Bo Jiang , Zhiwei Miao . Research Progress in Enantioselective Synthesis of Axial Chiral Compounds. University Chemistry, 2024, 39(11): 158-173. doi: 10.12461/PKU.DXHX202403106
11. [11]
  Conghao Shi , Ranran Wang , Juli Jiang , Leyong Wang . The Illustration on Stereoisomers of Macrocycles Containing Multiple Chiral Centers via Tröger Base-based Macrocycles. University Chemistry, 2024, 39(7): 394-397. doi: 10.3866/PKU.DXHX202311034
12. [12]
  Heng Chen , Longhui Nie , Kai Xu , Yiqiong Yang , Caihong Fang . 两步焙烧法制备大比表面积和结晶性增强超薄g-C₃N₄纳米片及其高效光催化产H₂O₂. Acta Physico-Chimica Sinica, 2024, 40(11): 2406019-. doi: 10.3866/PKU.WHXB202406019
13. [13]
  Tingyu Zhu , Hui Zhang , Wenwei Zhang . Exploration and Practice of Ideological and Political Education in the Course of Experiments on Chemical Functional Molecules: Synthesis and Catalytic Performance Study of Chiral Mn(III)Cl-Salen Complex. University Chemistry, 2024, 39(4): 75-80. doi: 10.3866/PKU.DXHX202311011
14. [14]
  Yan Li , Xinze Wang , Xue Yao , Shouyun Yu . 基于激发态手性铜催化的烯烃E→Z异构的动力学拆分——推荐一个本科生综合化学实验. University Chemistry, 2024, 39(5): 1-10. doi: 10.3866/PKU.DXHX202309053
15. [15]
  Xinyu Yin , Haiyang Shi , Yu Wang , Xuefei Wang , Ping Wang , Huogen Yu . Spontaneously Improved Adsorption of H₂O and Its Intermediates on Electron-Deficient Mn^(3+δ)+ for Efficient Photocatalytic H₂O₂ Production. Acta Physico-Chimica Sinica, 2024, 40(10): 2312007-. doi: 10.3866/PKU.WHXB202312007
16. [16]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
17. [17]
  Guanghui SUI , Yanyan CHENG . Application of rice husk-based activated carbon-loaded MgO composite for symmetric supercapacitors. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 521-530. doi: 10.11862/CJIC.20240221
18. [18]
  Hualin Jiang , Wenxi Ye , Huitao Zhen , Xubiao Luo , Vyacheslav Fominski , Long Ye , Pinghua Chen . Novel 3D-on-2D g-C₃N₄/AgI._x._y heterojunction photocatalyst for simultaneous and stoichiometric production of H₂ and H₂O₂ from water splitting under visible light. Chinese Chemical Letters, 2025, 36(2): 109984-. doi: 10.1016/j.cclet.2024.109984
19. [19]
  Yanglin Jiang , Mingqing Chen , Min Liang , Yige Yao , Yan Zhang , Peng Wang , Jianping Zhang . Experimental and Theoretical Investigations of Solvent Polarity Effect on ESIPT Mechanism in 4′-N,N-diethylamino-3-hydroxybenzoflavone. Acta Physico-Chimica Sinica, 2025, 41(2): 100012-. doi: 10.3866/PKU.WHXB202309027
20. [20]
  Jiying Liu , Zehua Li , Wenjing Zhang , Donghui Wei . Molecular Orbital and Nucleus-Independent Chemical Shift Calculations for C₆H₆ and B₁₂H₁₂^2-: A Computational Chemistry Experiment. University Chemistry, 2025, 40(3): 186-192. doi: 10.12461/PKU.DXHX202406085

Get Citation

PDF

XML

Metrics

PDF Downloads(698)
Abstract views(1472)
HTML views(43)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Experimental Test of“Parity-Time Asymmetry”in Electron Spin-Flip Raman Scattering of the N+H…O Hydrogen Bond in Chiral Alanine Crystals

Metrics

通讯作者: 陈斌, bchen63@163.com

Experimental Test of“Parity-Time Asymmetry”in Electron Spin-Flip Raman Scattering of the N⁺H…O Hydrogen Bond in Chiral Alanine Crystals