论文标题
阻碍转子的拉曼信号
The raman signal of a hindered rotor
论文作者
论文摘要
我们提出了一种计算量子固体固体氢和氘的拉曼模式的方法。我们使用平均场假设,即定量激发位于一个分子上。这是通过在角度依赖性电势中的时间依赖性Schroedinger方程的明确解和极化的直接计算来完成的。我们表明,在自由行限制中,h $ _2 $和d $ _2 $频率的频率有2倍,它朝着$ \ sqrt {2} $进化,因为模式由于更强的交互而获得了图书馆字符。如果Anharmonic术语削弱了谐波电位,则该比率超出了$ \ sqrt {2} $。我们还使用密度功能理论和分子动力学来计算E $ _ {2_G} $光学声子频率和拉曼线宽。分子动力学表明,除了在非常低的压力和高温下,分子不是游离转子,并且随着II期接近时的振荡器。我们适合实验频率的相互作用强度,但是对强度的良好一致性也要求我们还包括强烈的首选定向,并在S $ _0 $(1)和S $ _0 $(0)贡献之间刺激了拉曼效应。不能再现了II期的实验拉曼光谱,表明在这种情况下,平均场假设无效。
We present a method for calculation of Raman modes of the quantum solid phase I solid hydrogen and deuterium. We use the mean-field assumption that the quantised excitations are localized on one molecule. This is done by explicit solution of the time-dependent Schroedinger equation in an angle-dependent potential, and direct calculation of the polarisation. We show that in the free-rotor limit, the H$_2$ and D$_2$ frequencies differ by a factor of 2, which evolves toward $\sqrt{2}$ as the modes acquire librational character due to stronger interactions. The ratio overshoots $\sqrt{2}$ if anharmonic terms weaken the harmonic potential. We also use density functional theory and molecular dynamics to calculate the E$_{2_g}$ optical phonon frequency and the Raman linewidths. The molecular dynamics shows that the molecules are not free rotors except at very low pressure and high temperature, and become like oscillators as phase II is approached. We fit the interaction strengths to experimental frequencies, but good agreement for intensities requires us to also include strong preferred-orientation and stimulated Raman effects between S$_0$(1) and S$_0$(0) contributions. The experimental Raman spectrum for phase II cannot be reproduced, showing that the mean-field assumption is invalid in that case.