Hasecke Lukas, Breitenbach Maximilian, Gimferrer Martí, Oswald Rainer, Mata Ricardo A
Institute of Physical Chemistry, University of Göttingen, Tammannstrasse 6, 37077 Göttingen, Germany.
J Phys Chem A. 2025 Apr 17;129(15):3560-3566. doi: 10.1021/acs.jpca.5c00382. Epub 2025 Apr 7.
In this contribution we present the first local density-fitted multicomponent density functional theory implementation and assess its use for the calculation of anharmonic zero-point energies. Four challenging cases of molecular aggregates are reviewed: deprotonated formic acid trimer, diphenyl ether--butyl alcohol conformers, anisole/methanol and anisole/2-naphtol dimers. These are all cases where a mismatch between the low-temperature computationally predicted minimum and the experimentally determined structure was observed. Through the use of nuclear-electronic orbital energies in the thermodynamic correction, the correct energetic ordering is recovered. For the smallest system, we compare our results to vibrational perturbation theory anharmonically corrected zero-point energy, with perfect agreement for the lower-lying conformers. The performance of the newly developed code and the density fitting errors are also analyzed. Overall, the new implementation shows a very good scaling with system size and the density fitting approximations exhibit a negligible impact.
在本论文中，我们展示了首个局部密度拟合多组分密度泛函理论的实现，并评估了其在计算非谐零点能方面的应用。回顾了四个具有挑战性的分子聚集体案例：去质子化甲酸三聚体、二苯醚 - 丁醇构象异构体、苯甲醚/甲醇和苯甲醚/2 - 萘酚二聚体。这些都是在低温下计算预测的最低能量结构与实验确定的结构不匹配的案例。通过在热力学校正中使用核 - 电子轨道能量，恢复了正确的能量排序。对于最小的体系，我们将结果与经非谐校正的零点能的振动微扰理论进行了比较，对于能量较低的构象异构体有完美的一致性。还分析了新开发代码的性能以及密度拟合误差。总体而言，新的实现方法显示出与系统大小非常好的缩放关系，并且密度拟合近似的影响可忽略不计。
