“宇称-时间不对称”的实验探索: 手性丙氨酸单晶N<sup>+</sup>H…O氢键的电子自旋翻转相变的不对称拉曼散射

引用本文: 王文清, 龚, 沈新春, 张玉凤. “宇称-时间不对称”的实验探索: 手性丙氨酸单晶N⁺H…O氢键的电子自旋翻转相变的不对称拉曼散射[J]. 物理化学学报, 2013, 29(03): 473-478. doi: 10.3866/PKU.WHXB201212273 shu

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

“宇称-时间不对称”的实验探索: 手性丙氨酸单晶N⁺H…O氢键的电子自旋翻转相变的不对称拉曼散射

基金项目:
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)

摘要:

手性丙氨酸单晶的极性N⁺H…O氢键在~270 K的自发对称性破缺, 可用变温拉曼振动光谱在b(cc)b几何条件下在线测定. 由于其对手性的灵敏度, 可以测定D-和L-丙氨酸的N⁺H…O氢键在电子自旋翻转相变时的微小能差. 晶体定向能量的正/负, 在于电子自旋的上/下转向, 取决于原子内在磁场的方向. 变温拉曼振动光谱可以观察到: 在D-和L-丙氨酸单晶之间, 拉曼散射光子的波数位移方向相反, 散射光子的不对称度约为1/3. 由于自旋是轴矢量, 样品必须是单晶, 沿轴向测定. 多晶粉末不能观察到相变. 与次甲基(C_α－H)在260 K的自旋翻转相变, 用变温拉曼振动光谱在c(aa)c 几何条件下的相对测量结果接近一致. 本实验提供了一条证明真实手性和“宇称-时间(PT)不对称”的新线索.

关键词:

English

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: 25 February 2013
Fund Project:
国家自然科学基金(21002006, 20452002)

国家科技部基础研究重大项目(2004-973-36)资助

Abstract:

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.

Key words:

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“宇称-时间不对称”的实验探索: 手性丙氨酸单晶N⁺H…O氢键的电子自旋翻转相变的不对称拉曼散射

English

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

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“宇称-时间不对称”的实验探索: 手性丙氨酸单晶N+H…O氢键的电子自旋翻转相变的不对称拉曼散射

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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

中国化学会秘书处

“宇称-时间不对称”的实验探索: 手性丙氨酸单晶N⁺H…O氢键的电子自旋翻转相变的不对称拉曼散射

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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