Comprehensive Assessment of GFN Tight-Binding and Composite Density Functional Theory Methods for Calculating Gas-Phase Infrared Spectra.
Comprehensive Assessment of GFN Tight-Binding and Composite Density Functional Theory Methods for Calculating Gas-Phase Infrared Spectra.
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DOI：
10.1021/acs.jctc.0c00877
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发表时间：
2020-11-10
影响因子：
5.5
通讯作者：
Grimme S
中科院分区：
文献类型：
--
作者：
Pracht P;Grant DF;Grimme S
振动光谱是表征化学物质的一种有价值和广泛使用的分析工具。通过与实验和低成本密度泛函理论(B3LYP-3c)的比较，研究了半经验量子力学GFN紧束缚方法和力场方法计算气相红外光谱的性能。使用7247个实验参考数据集来评估基于自动光谱比较的方法性能。采用各种定量光谱相似性度量方法对理论和实验进行了比较，并确定了经验标度因子。结果表明，原子质量标度为密度泛函理论和半经验计算中的标准全局频率标度提供了一种准确而简单的替代方法。此外，对58个典型的过渡金属配合物的方法性能进行了研究。在本工作中介绍的高效DFT合成方法B3LYP-3c被发现非常适合于一般的红外光谱计算。GFN1和GFN2-XTB紧密捆绑方法的表现明显好于PMX竞争对手。研究了数据子集的构象变化，发现对模拟光谱的影响一般，这表明在自动化合物鉴定工作流程中，相应的详细采样步骤可能被忽略。
Vibrational spectroscopy is a valuable and widely used analytical tool for the characterization of chemical substances. We investigate the performance of semiempirical quantum mechanical GFN tight-binding and force-field methods for the calculation of gas-phase infrared spectra in comparison to experiment and low-cost (B3LYP-3c) density functional theory. A data set of 7247 experimental references was used to evaluate method performance based on automatic spectra comparison. Various quantitative spectral similarity measures were employed for the comparison between theory and experiment and for determining empirical scaling factors. It is shown that the scaling of atomic masses provides an accurate yet simple alternative to standard global frequency scaling in density functional theory (DFT) and semiempirical calculations. Furthermore, the method performance for 58 exemplary transition metal complexes was investigated. The efficient DFT composite method B3LYP-3c, that was introduced in the course of this work, was found to be excellently suited for general IR spectra calculations. The GFN1- and GFN2-xTB tight-binding methods clearly outperformed the PMx competitors. Conformational changes were investigated for a subset of the data and are found to have a mediocre strong influence on the simulated spectra suggesting that the corresponding elaborate sampling steps may be neglected in automated compound identification workflows.
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影响因子：
6.2
作者：
Baumann, K;Clerc, JT
通讯作者：
Clerc, JT
影响因子：
8.4
作者：
Gastegger M;Behler J;Marquetand P
通讯作者：
Marquetand P
DOI：
10.6028/jres.104.004
发表时间：
1999-02-01
影响因子：
1.5
作者：
Chu PM;Guenther FR;Rhoderick GC;Lafferty WJ
通讯作者：
Lafferty WJ
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
1.7
作者：
BLOM, CE;OTTO, LP;ALTONA, C
通讯作者：
ALTONA, C