Quantitative Comparison of Experimental and Computed IR-Spectra Extracted from Ab Initio Molecular DynamicsClick to copy article linkArticle link copied!
- Beatriz von der EschBeatriz von der EschChair of Theoretical Chemistry, Department of Chemistry, University of Munich (LMU), Butenandtstr. 7, D-81377 München, GermanyMore by Beatriz von der Esch
- Laurens D. M. PetersLaurens D. M. PetersChair of Theoretical Chemistry, Department of Chemistry, University of Munich (LMU), Butenandtstr. 7, D-81377 München, GermanyMore by Laurens D. M. Peters
- Lena SauerlandLena SauerlandChair of Theoretical Chemistry, Department of Chemistry, University of Munich (LMU), Butenandtstr. 7, D-81377 München, GermanyMore by Lena Sauerland
- Christian Ochsenfeld*Christian Ochsenfeld*Email: [email protected]Chair of Theoretical Chemistry, Department of Chemistry, University of Munich (LMU), Butenandtstr. 7, D-81377 München, GermanyMore by Christian Ochsenfeld
Abstract
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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