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Determination of vibrational polarizabilities and hyperpolarizabilities using field-induced coordinates

机译:使用场致坐标确定振动极化率和超极化率

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摘要

An analytical set of field-induced coordinates is defined and is used to show that the vibrational degrees of freedom required to completely describe nuclear relaxation polarizabilities and hyperpolarizabilities is reduced from 3N-6 to a relatively small number. As this number does not depend upon the size of the molecule, the process provides computational advantages. A method is provided to separate anharmonic contributions from harmonic contributions as well as effective mechanical from electrical anharmonicity. The procedures are illustrated by Hartree-Fock calculations, indicating that anharmonicity can be very important
机译:定义了一组场感应坐标的分析,并用于显示完全描述核弛豫极化率和超极化率所需的振动自由度从3N-6减少到相对较小的数。由于该数目不取决于分子的大小,因此该方法具有计算优势。提供了一种从谐波贡献中分离非谐波贡献以及从电气非谐波中分离有效机械的方法。 Hartree-Fock计算说明了该过程,表明非谐性可能非常重要

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