Bond Lengths and Dipole Moments of Diatomic Molecules under Isotropic Pressure with the XP-PCM and GOSTSHYP Models,Journal of Chemical Theory and Computation

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Bond Lengths and Dipole Moments of Diatomic Molecules under Isotropic Pressure with the XP-PCM and GOSTSHYP Models
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-08-27 , DOI: 10.1021/acs.jctc.4c00665
Jochen Eeckhoudt ₁ , Mercedes Alonso ₁ , Paul Geerlings ₁ , Frank De Proft ₁

Affiliation

While high-pressure chemistry has a well-established history, methods to simulate pressure at the single-molecule level have been somewhat lacking. The current work aims at comparing two static models (XP-PCM and GOSTSHYP) to apply isotropic pressure to single molecules, focusing on the equilibrium bond length and electric dipole moment of diatomic molecules. Numerical challenges arising in the potential energy surface using the XP-PCM method were examined, and a pragmatic approach was followed to mitigate these. The definition of the cavity was scrutinized, and two approaches to retrieve the isotropic character that could potentially be lost when using the standard methodology were suggested. Subsequently, equilibrium bond lengths under pressure were evaluated, showing reasonable agreement between GOSTSHYP and XP-PCM, but some discrepancies persist. A Taylor series analysis introduced elsewhere was then applied to rationalize the observed trends in terms of the bond surface. Finally, the dipole moment was shown to be highly sensitive to the cavity definition, and qualitative agreement necessitates the use of our adapted procedure.

中文翻译：

使用 XP-PCM 和 GOSTSHYP 模型计算各向同性压力下双原子分子的键长和偶极矩

虽然高压化学有着悠久的历史，但在单分子水平上模拟压力的方法却一直缺乏。目前的工作旨在比较对单分子施加各向同性压力的两种静态模型（XP-PCM 和 GOSTSHYP），重点关注双原子分子的平衡键长和电偶极矩。使用 XP-PCM 方法检查了势能面中出现的数值挑战，并采用了实用的方法来缓解这些挑战。对空腔的定义进行了仔细检查，并提出了两种恢复各向同性特征的方法，这些特征在使用标准方法时可能会丢失。随后，评估了压力下的平衡键长，显示 GOSTSHYP 和 XP-PCM 之间相当一致，但仍然存在一些差异。然后应用其他地方引入的泰勒级数分析来合理化观察到的粘合表面趋势。最后，偶极矩被证明对腔定义高度敏感，并且定性一致性需要使用我们调整的程序。

更新日期：2024-08-27

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