ANALYSIS OF TORSIONAL SPECTRA OF MOLECULES WITH 2 INTERNAL C3V ROTORS .13. VIBRATIONAL ASSIGNMENTS, TORSIONAL POTENTIAL FUNCTIONS, AND GAS-PHASE THERMODYNAMIC FUNCTIONS OF ISOPROPYLAMINE-D0 AND ISOPROPYLAMINE-D2
ANALYSIS OF TORSIONAL SPECTRA OF MOLECULES WITH 2 INTERNAL C3V ROTORS .13. VIBRATIONAL ASSIGNMENTS, TORSIONAL POTENTIAL FUNCTIONS, AND GAS-PHASE THERMODYNAMIC FUNCTIONS OF ISOPROPYLAMINE-D0 AND ISOPROPYLAMINE-D2
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DOI：
10.1021/j100473a016
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发表时间：
1979-01-01
影响因子：
--
通讯作者：
COMPTON, DAC
中科院分区：
文献类型：
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作者：
DURIG, JR;GUIRGIS, GA;COMPTON, DAC
本文研究了气体、液体和固体的拉曼光谱，以及气体和固体异丙胺-d0和“d2”在4000-50 cm之间的红外光谱。用低能S反式构象和高能反式构象之间的平衡解释了固相光谱和液体相光谱的不同，并对S反式构象进行了完整的振动归属。气态化合物的远红外光谱包含由于不对称氨基和耦合的甲基扭转而产生的谱带；这些谱带的分配是通过观察到每个振动模式的两个量子跃迁来辅助的。计算了不对称势能函数，得到-d0和-d2化合物在气相中的构象热差分别为446和523卡/摩尔。计算了异丙胺-d0的甲基扭转势函数，得到甲基转子内旋的势垒高度为4.23±0.06千卡/摩尔。在一定的温度范围内计算了理想气体热力学函数值。
The Raman spectra of gaseous, liquid, and solid, and infrared spectra of gaseous and solid isopropylamine-d0 and" d2 have been investigated between 4000 and 50cm" 1. Differences between the spectrum of the solid phase and that of the fluid phases have been interpreted in terms of an equilibrium between low energy s-trans and high energygauche conformers, and a complete vibrational assignment has been proposed for the s-trans conformer. The far-infrared spectra of the gaseous compounds contained bands due to the asymmetric amino and coupled methyl torsions; the assignment of these bands was aided by observation of a number of two quantum transitions for each vibrational mode. The asymmetric potential functions were calculated which resulted in values for the enthalpy differences between conformers in the gaseous phase of 446 and 523 cal/mol for the-d0 and-d2 compounds, respectively. The methyl torsional potentialfunction of isopropylamine-d0 was calculated which led to a value for the barrier height to internal rotation of the methyl rotors of 4.23±0.06 kcal/mol. Values for the ideal gas thermodynamic functions have been calculated over a range of temperatures.