在振动自洽场处理中大幅降低的网格密度不会对所得波数产生显著影响。

Largely reduced grid densities in a vibrational self-consistent field treatment do not significantly impact the resultingwavenumbers.

作者信息

Lutz Oliver M D, Rode Bernd M, Bonn Günther K, Huck Christian W

机构信息

Institute of Analytical Chemistry and Radiochemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, Innsbruck 6020, Austria.

Institute of General, Inorganic and Theoretical Chemistry, Center for Chemistry and Biomedicine, University of Innsbruck, Innrain 80-82, Innsbruck 6020, Austria.

出版信息

Molecules. 2014 Dec 17;19(12):21253-75. doi: 10.3390/molecules191221253.

DOI:10.3390/molecules191221253

PMID:25525825

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6270979/

Abstract

Especially for larger molecules relevant to life sciences, vibrational self-consistent field (VSCF) calculations can become unmanageably demanding even when only first and second order potential coupling terms are considered. This paper investigates to what extent the grid density of the VSCF's underlying potential energy surface can be reduced without sacrificing accuracy of the resulting wavenumbers. Including single-mode and pair contributions, a reduction to eight points per mode did not introduce a significant deviation but improved the computational efficiency by a factor of four. A mean unsigned deviation of 1.3% from the experiment could be maintained for the fifteen molecules under investigation and the approach was found to be applicable to rigid, semi-rigid and soft vibrational problems likewise. Deprotonated phosphoserine, stabilized by two intramolecular hydrogen bonds, was investigated as an exemplary application.

摘要

特别是对于与生命科学相关的大分子，即使仅考虑一阶和二阶势能耦合项，振动自洽场（VSCF）计算的要求也可能变得难以处理。本文研究了在不牺牲所得波数准确性的前提下，VSCF潜在能量表面的网格密度可以降低到何种程度。包括单模和对贡献，将每个模式减少到八个点不会引入显著偏差，但计算效率提高了四倍。对于所研究的15个分子，可以保持与实验的平均无符号偏差为1.3%，并且发现该方法同样适用于刚性、半刚性和软振动问题。作为一个示例性应用，研究了通过两个分子内氢键稳定的去质子化磷酸丝氨酸。