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Vibrational effects on surface energies and band gaps in hexagonal and cubic ice

机译:振动对六角形和立方冰表面能和带隙的影响

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Surface energies of hexagonal and cubic water ice are calculated using first-principles quantum mechanical methods, including an accurate description of anharmonic nuclear vibrations. We consider two proton-orderings of the hexagonal and cubic ice basal surfaces and three proton-orderings of hexagonal ice prism surfaces, finding that vibrations reduce the surface energies by more than 10%. We compare our vibrational densities of states to recent sum frequency generation absorption measurements and identify surface proton-orderings of experimental ice samples and the origins of characteristic absorption peaks. We also calculate zero point quantum vibrational corrections to the surface electronic band gaps, which range from -1.2 eV for the cubic ice basal surface up to -1.4 eV for the hexagonal ice prism surface. The vibrational corrections to the surface band gaps are up to 12% smaller than for bulk ice. Published by AIP Publishing.
机译:六方和立方水冰的表面能是使用第一性原理量子力学方法计算的,其中包括对非谐核振动的准确描述。我们考虑了六边形和立方冰基表面的两个质子有序和六边形冰棱柱表面的三个质子有序,发现振动将表面能降低了10%以上。我们将状态的振动密度与最近的总和频率生成吸收测量值进行比较,并确定实验冰样品的表面质子有序化和特征吸收峰的起源。我们还计算了对表面电子带隙的零点量子振动校正,其范围从立方冰底表面的-1.2 eV到六角形冰棱镜表面的-1.4 eV。表面带隙的振动校正比散装冰小12%。由AIP Publishing发布。

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