涨落电荷模型下分子间电荷转移的尺寸扩展极化率
Size-extensive polarizabilities with intermolecular charge transfer in a fluctuating-charge model
摘要：
在分子力学方法中，涨落电荷模型已被用来模拟极化效应。然而，他们高估了大系统的极化率。以前的补救措施是以禁止分子间电荷转移为代价的。在这里，我们调查这种缺乏的尺寸扩展性，并表明，忽视的条款所产生的电荷守恒是部分负责，这些条款也是至关重要的保持正确的平移对称性的偶极矩和极化率，经典静电理论的要求。此外，QTPIE演示线性标度极化率耦合的外部电场的方式，将其潜在的原子电负性的扰动时。因此，第一次，我们有一个波动的电荷模型，预测尺寸广泛的偶极极化率，但允许分子间的电荷转移。
英文摘要：
Fluctuating-charge models have been used to model polarization effects in molecular mechanics methods. However, they overestimate polarizabilities in large systems. Previous attempts to remedy this have been at the expense of forbidding intermolecular charge-transfer. Here, we investigate this lack of size-extensivity and show that the neglect of terms arising from charge conservation is partly responsible; these terms are also vital for maintaining the correct translational symmetries of the dipole moment and polarizability that classical electrostatic theory requires. Also, QTPIE demonstrates linear-scaling polarizabilities when coupling the external electric field in a manner that treats its potential as a perturbation of the atomic electronegativities. Thus for the first time, we have a fluctuating-charge model that predicts size-extensive dipole polarizabilities, yet allows intermolecular charge-transfer.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
