从头算
谱线
NIST公司
计算机科学
相似性(几何)
分子动力学
缩放比例
水准点(测量)
化学
统计物理学
计算物理学
人工智能
物理
计算化学
数学
图像(数学)
量子力学
大地测量学
有机化学
自然语言处理
地理
几何学
作者
Beatriz von der Esch,Laurens D. M. Peters,Lena Sauerland,Christian Ochsenfeld
标识
DOI:10.1021/acs.jctc.0c01279
摘要
Experimentally measured infrared spectra are often compared to their computed equivalents. However, the accordance is typically characterized by visual inspection, which is prone to subjective judgment. The primary challenge for a similarity-based analysis is that the artifacts introduced by each approach are very different and, therefore, may require preprocessing steps to determine and correct impeding irregularities. To allow for automated objective assessment, we propose a practical and comprehensive workflow involving scaling factors, a novel baseline correction scheme, and peak smoothing. The resulting spectra can then easily be compared quantitatively using similarity measures, for which we found the Pearson correlation coefficient to be the most suitable. The proposed procedure is then applied to compare the agreement of the experimental infrared spectra from the NIST Chemistry Web book with the calculated spectra using standard harmonic frequency analysis and spectra extracted from ab initio molecular dynamics simulations at different levels of theory. We conclude that the direct, quantitative comparison of calculated and measured IR spectra might become a novel, sophisticated approach to benchmark quantum-chemical methods. In the present benchmark, simulated spectra based on ab initio molecular dynamics show in general better agreement with the experiment than static calculations.
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