Citation: WANG Wen-Qing, SHEN Xin-Chun, WU Ji-Lan, NG Yan, SHEN Guo-Hua, ZHAO Hong-Kai. Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N⁺H…O^- Bond in Chiral Alanine Crystal[J]. Acta Physico-Chimica Sinica, ;2012, 28(04): 773-780. doi: 10.3866/PKU.WHXB201202132 shu

Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N⁺H…O^- Bond in Chiral Alanine Crystal

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 Chemistry and Chemical Engineering, Shandong University, Jinan 250061, P. R. China

Received Date: 31 October 2011
Available Online: 13 February 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)

With a view to understanding the argument of phase-transition mechanisms of D- and L-alanine at around 270 K, the temperature dependence of heat capacity measurements was investigated, for single crystals, ground powders, and polycrystalline products, using differential scanning calorimetry (DSC). The C_p (heat capacity under constant pressure) values of D- and L-alanine were calibrated with standard sapphire by the triple-curve method; these values coincide with the standard C_p values in the literature. Endothermic transition peaks were observed at T_c=272.02 K, ΔH=1.87 J·mol^-1 and T_c=271.85 K, ΔH=1.46 J·mol^-1 for D- and L- alanine, respectively, and T_c=273.59 K, ΔH=1.75 J·mol^-1 and T_c=273.76 K, ΔH=1.57 J·mol^-1 for the reference crystals D- and L-valine, respectively. The energy differences of 0.41 J· mol^-1 for D-and L-alanine and 0.18 J·mol^-1 for D- and L-valine, which were observed from pre-aligned molecules in the single crystals and vanished in the ground powders and polycrystalline products, show that the phase transition is related to the crystal lattice. Neutron diffraction results exclude the possibility of a D→L configuration change, and show that the hydrogen bonds run antiparallel to the c-axis in the D- and Lcrystals. Polarized Raman vibrational spectroscopy shows that the transition mechanism may be related to the electronic orbital angular momentum and magnetic dipole moments of N⁺H…O^- in the crystals. External magnetic fields, H=+1, -1 T, were applied parallel to the c(z)-axis of the D- and L-alanine crystalline lattices, respectively. The DC-magnetic susceptibilities show electron spin-flip transitions at around 270 K in D- and L-alanine. The spin is“up”or“down”relative to the direction of N⁺H…O^- bond along the c(z)-axis. Based on spin rigidity and magnetic anisotropy, the results help to explain the discrepancies among heat capacity and magnetic susceptibility data for single crystals and polycrystalline powders of D- and L-alanine.
- Heat capacity,
- DC-magnetic susceptibility,
- N⁺H…O^- bonding,
- Electron spin-flip,
- Asymmetry transition,
- D- and L-alanine crystals
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沈阳化工大学材料科学与工程学院沈阳 110142

Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N+H…O- Bond in Chiral Alanine Crystal

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通讯作者: 陈斌, bchen63@163.com

Heat Capacity and DC-Magnetic Susceptibility Evidence for the Asymmetry of Electron Spin-Flip Phase Transition of N⁺H…O^- Bond in Chiral Alanine Crystal