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Vibrational and thermal effects on the dipole polarizability of methane and carbon tetrachloride from vibrational structure calculations

机译:通过振动结构计算,振动和热对甲烷和四氯化碳的偶极极化率的影响

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摘要

We present a theoretical study of vibrational and thermal effects on the dipole polarizability of methane and carbon tetrachloride.Using a fourth order Taylor expansion in rectilinear normal coordinates of the potential and property surfaces we solve the vibrational problem using vibrational structure theory,e.g.,through vibrational self-consistent-field or vibrational configuration-interaction theory.For each vibrational state we calculate in addition the vibrational state average polarizability.Constructing the vibrational partition function by"brute force"allows for prediction of thermal effects on the dipole polarizability.The method is not restricted in any way to polarizabilities nor to the specific representation of the potential and property surfaces employed in this work.Any molecular property with a suitable normal coordinate representation may be considered.We discuss the performance of vibrational self-consistent field as compared to vibrational configuration interaction and study in detail the convergence of the former method with respect to the number of vibrational states included in the thermal averaging.Based on calculations including up to 170 000 vibrational self-consistent-field states we present thermal effects on the dipole polarizability of methane and carbon tetrachloride in the temperature ranges 0-1100 and 0-500 K,respectively.The predicted thermal effect on the dipole polarizability of methane is found to be ~0.8% which compare well with previous experimental measurements.
机译:我们提供了振动和热效应对甲烷和四氯化碳的偶极极化性的理论研究。在势能和特性面的直线法向坐标中使用四阶泰勒展开,我们使用振动结构理论(例如通过振动)解决了振动问题。自洽场或振动构型相互作用理论。对于每种振动状态,我们还计算振动状态的平均极化率。通过“蛮力”构造振动分配函数可以预测热对偶极子极化率的影响。该方法是既不限于极化率,也不限于本工作中使用的势能和特性表面的特定表示形式。可以考虑具有适当法向坐标表示形式的任何分子性质。我们讨论了与振动相比,振动自洽场的性能配置交互和d详细研究了前一种方法相对于热平均中包含的振动状态数量的收敛性。基于包括多达170 000个振动自洽场状态的计算,我们介绍了热对甲烷和偶极子极化率的影响。分别在0-1100和0-500 K的温度范围内测量四氯化碳。发现对甲烷的偶极可极化性的预测热效应为〜0.8%,与先前的实验测量结果相比较。

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