Accurate Vibrational and Ro-Vibrational Contributions to the Properties of Large Molecules by a New Engine Employing Curvilinear Internal Coordinates and Vibrational Perturbation Theory to Second Order,Journal of Chemical Theory and Computation

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Accurate Vibrational and Ro-Vibrational Contributions to the Properties of Large Molecules by a New Engine Employing Curvilinear Internal Coordinates and Vibrational Perturbation Theory to Second Order
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-08-31 , DOI: 10.1021/acs.jctc.4c00857
Marco Mendolicchio ₁ , Vincenzo Barone ₂

Affiliation

The unbiased comparison between theory and experiment requires approaches more sophisticated than the basic harmonic-oscillator rigid-rotor model, for taking into account vibrational averaging effects and ro-vibrational couplings in molecules of increasing size. Second-order vibrational perturbation theory based on curvilinear internal coordinates (ICs) offers a remarkable compromise between accuracy and computational cost, thanks to the reduction of mode–mode couplings with respect to their counterparts based on Cartesian coordinates. Therefore, we have developed, implemented, and validated a general engine employing ICs, which allows the accurate evaluation of vibrational averages and ro-vibrational couplings for molecules containing up to about 50 atoms beyond the harmonic approximation. After validation of the new tool for relatively small molecules, the effectiveness of ICs has been demonstrated for some flexible and/or quite large molecular bricks of life.

中文翻译：

采用曲线内坐标和二阶振动摄动理论的新型发动机对大分子特性的精确振动和旋转振动贡献

理论与实验之间的公正比较需要比基本谐波振荡器刚性转子模型更复杂的方法，以考虑尺寸增加的分子中的振动平均效应和旋转振动耦合。基于曲线内坐标 (IC) 的二阶振动摄动理论在精度和计算成本之间提供了显着的折衷，这要归功于相对于基于笛卡尔坐标的对应物减少了模-模耦合。因此，我们开发、实施并验证了一种采用 IC 的通用引擎，它可以准确评估含有最多约 50 个原子（超出谐波近似）的分子的振动平均值和旋转振动耦合。在对相对较小分子的新工具进行验证后，IC 的有效性已在一些灵活和/或相当大的分子生命砖中得到证明。

更新日期：2024-08-31

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