Rakvin B, Maltar-Strmecki N, Ramsey C M, Dalal N S
Ruder Bosković Institute, P.O. Box 180, 10002, Zagreb, Croatia.
J Chem Phys. 2004 Apr 8;120(14):6665-73. doi: 10.1063/1.1666107.
With the view of understanding the low frequency (40-50 cm(-1)) motional processes in L-alanine around 4 K, we have carried out heat capacity (CP) and electron spin echo (ESE) measurements on L-alanine and L-alanine-d7. The obtained CP data show the so-called boson peak (seen as a maximum in CP/T3 versus T plots) in the low temperature region (1.8-20 K). The phase memory time, T(M), and spin lattice relaxation time, T1, of the spin probe, the so-called first stable alanine radical (SAR1), *CHCH3COOH, have been measured between 4 and 105 K. The obtained relaxation rate 1/T1 shows an anomalous increase which coincides with the emergence of a boson peak in the low temperature region (4-20 K). Together, the ESE and the CP data confirm the existence of a thermally activated dynamic orientational disorder in the lattices of both compounds below 20 K. The results help explain the discrepancy between the CP data from powders and single crystals of alanine, as well as the proanomalous relaxation mechanisms for SAR1 in these lattices, and they also provide a mechanism for the spin-lattice relaxation process for SAR1 at cryogenic temperatures.
为了理解4K左右L-丙氨酸中低频(40 - 50cm⁻¹)的运动过程,我们对L-丙氨酸和L-丙氨酸-d7进行了热容(CP)和电子自旋回波(ESE)测量。所获得的CP数据在低温区域(1.8 - 20K)显示出所谓的玻色子峰(在CP/T³对T的图中表现为最大值)。自旋探针即所谓的第一个稳定丙氨酸自由基(SAR1),*CHCH3COOH的相位记忆时间T(M)和自旋晶格弛豫时间T1在4至105K之间进行了测量。所获得的弛豫率1/T1显示出异常增加,这与低温区域(4 - 20K)中玻色子峰的出现相吻合。ESE和CP数据共同证实了两种化合物晶格在20K以下存在热激活的动态取向无序。这些结果有助于解释丙氨酸粉末和单晶的CP数据之间的差异,以及这些晶格中SAR1的前异常弛豫机制,并且它们还为低温下SAR1的自旋晶格弛豫过程提供了一种机制。