A quantitative assessment of deformation energy in intermolecular interactions: How important is it?
A quantitative assessment of deformation energy in intermolecular interactions: How important is it?
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DOI：
10.1063/5.0155895
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发表时间：
2023-06
期刊：
影响因子：
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通讯作者：
Caroline T Sargent;Raina Kasera;Zachary L Glick;C. Sherrill;D. Cheney
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文献类型：
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作者：
Caroline T Sargent;Raina Kasera;Zachary L Glick;C. Sherrill;D. Cheney
二聚体相互作用能已经在计算化学中得到了很好的研究，但它们可以提供依赖于系统的分子结合的不完全理解。在目前的研究中，我们提供了28个有机分子二聚体的焦点耦合簇相互作用和变形能（总和为结合能，De）的数据集。我们使用这些高度精确的能量来评估十个密度泛函近似的精度。采用双ζ基集的最佳方法B97M-D3BJ计算了104种有机二聚体的结合能，并分析了相互作用的性质和强度对变形能的影响。变形能可高达二聚体相互作用能的50%，特别是当氢键存在时。在大多数情况下，二聚体中存在的两个或多个氢键对应于-10至-25千卡摩尔-1的相互作用能，允许变形能高于1千卡摩尔-1（最高可达9.5千卡摩尔-1）。由于相互作用能较弱，缺乏氢键通常将变形能限制在1 kcal mol-1以下。
Dimer interaction energies have been well studied in computational chemistry, but they can offer an incomplete understanding of molecular binding depending on the system. In the current study, we present a dataset of focal-point coupled-cluster interaction and deformation energies (summing to binding energies, De) of 28 organic molecular dimers. We use these highly accurate energies to evaluate ten density functional approximations for their accuracy. The best performing method (with a double-ζ basis set), B97M-D3BJ, is then used to calculate the binding energies of 104 organic dimers, and we analyze the influence of the nature and strength of interaction on deformation energies. Deformation energies can be as large as 50% of the dimer interaction energy, especially when hydrogen bonding is present. In most cases, two or more hydrogen bonds present in a dimer correspond to an interaction energy of -10 to -25 kcal mol-1, allowing a deformation energy above 1 kcal mol-1 (and up to 9.5 kcal mol-1). A lack of hydrogen bonding usually restricts the deformation energy to below 1 kcal mol-1 due to the weaker interaction energy.