论文标题
V30基准设置用于分子二聚体的非谐波振动频率
The V30 Benchmark Set for Anharmonic Vibrational Frequencies of Molecular Dimers
论文作者
论文摘要
分子间的振动非常具有挑战性,但是确定熵和自由能的最关键部分,例如,通过THZ光谱法启用了同一分子的不同晶体包装布置的区别。本文中,我们引入了一个基准数据集-V30-包含30个小分子二聚体,其间相互作用范围从仅限于van -waals散布到具有氢键的系统。所有计算均以量子化学CCSD(T)的黄金标准进行。我们讨论了通过不同模型获得的振动频率,从独立的Morse振荡器上的谐波近似开始到二阶振动摄动理论(VPT2),该振动频率允许适当的非谐波处理,包括振动模式的耦合。但是,许多低频间分子模式中存在的大幅度运动对于VPT2来说是有问题的。与经常使用的内部旋转处理相比,我们用简单的一维障碍转子模型代替了这种有问题的模式。我们将选定的二聚体与可用的实验数据或势能表面的高级计算进行了比较,并表明VPT2与阻碍转子结合使用,可以很好地描述涉及小型和半刚性分子的二聚体子集的基本频率。
Intermolecular vibrations are extremely challenging to describe but are the most crucial part for determining entropy and hence free energies, and enable for instance the distinction between different crystal-packing arrangements of the same molecule via THz spectroscopy. Herein, we introduce a benchmark data set - V30 - containing 30 small molecular dimers with intermolecular interactions ranging from exclusively van-der-Waals dispersion to systems with hydrogen bonds. All calculations are performed with the gold standard of Quantum Chemistry CCSD(T). We discuss vibrational frequencies obtained via different models starting with the harmonic approximation over independent Morse oscillators up to second-order vibrational perturbation theory (VPT2), which allows a proper anharmonic treatment including coupling of vibrational modes. However, large amplitude motions present in many low-frequency intermolecular modes are problematic for VPT2. In analogy to the often used treatment for internal rotations, we replace such problematic modes by a simple one-dimensional hindered rotor model. We compare selected dimers with available experimental data or high-level calculations of potential energy surfaces and show that VPT2 in combination with hindered rotors can yield a very good description of fundamental frequencies for the discussed subset of dimers involving small and semi-rigid molecules.