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

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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