Chemical Sciences Division, Lawrence Berkeley National Laboratory, University of California, Berkeley, Berkeley, California 94720, United States.
Kenneth S. Pitzer Center for Theoretical Chemistry, University of California, Berkeley, Berkeley, California 94720, United States.
J Phys Chem Lett. 2021 Dec 30;12(51):12360-12369. doi: 10.1021/acs.jpclett.1c03476. Epub 2021 Dec 22.
We report a linear combination of atomic dipole (LCAD) method for calculating the bond dipole moments of molecules. We show that the LCAD method reproduces the known molecular dipole moments of small to large molecules with a small error with respect to experimental and benchmark ab initio calculations, and molecular dipole distributions of bulk water that agree with maximally localized Wannier functions. The bond dipole moments derived from LCAD are also chemically interpretable in terms of the trend in bond ionicity in going from neutral to charged molecules. Moreover, the LCAD method accurately captures the influence of electric fields, supported by the correct trend in the change of the dipole moment under a uniform external electric field. The better grounding of bond dipole calculations indicates that it should also serve as a useful approach to bond dipole-field models used in catalysis or to reconstruct the small dipole of a H-terminated graphene flake.
我们报告了一种用于计算分子键偶极矩的原子偶极线性组合 (LCAD) 方法。我们表明，LCAD 方法能够以小的误差再现从小分子到大分子的已知分子偶极矩，与实验和基准从头算计算以及与最大局域化 Wannier 函数一致的体相水分子的分子偶极矩分布。根据从中性分子到带电分子的键离子性趋势，从 LCAD 得出的键偶极矩也具有化学可解释性。此外，LCAD 方法准确地捕捉到了电场的影响，这得到了在外加均匀电场下偶极矩变化的正确趋势的支持。键偶极计算的更好基础表明，它也应该是一种有用的方法，可用于催化作用中的键偶极-场模型，或重建 H 终止石墨烯薄片的小偶极矩。
