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Towards theoretical spectroscopy with error bars: systematic quantification of the structural sensitivity of calculated spectra

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Abstract

Molecular spectra calculated with quantum-chemical methods are subject to a number of uncertainties (e.g., errors introduced by the computational methodology) that hamper the direct comparison of experiment and computation. Judging these uncertainties is crucial for drawing reliable conclusions from the interplay of experimental and theoretical spectroscopy, but largely relies on subjective judgment. Here, we explore the application of methods from uncertainty quantification to theoretical spectroscopy, with the ultimate goal of providing systematic error bars for calculated spectra. As a first target, we consider distortions of the underlying molecular structure as one important source of uncertainty. We show that by performing a principal component analysis, the most influential collective distortions can be identified, which allows for the construction of surrogate models that are amenable to a statistical analysis of the propagation of uncertainties in the molecular structure to uncertainties in the calculated spectrum. This is applied to the calculation of X-ray emission spectra of iron carbonyl complexes, of the electronic excitation spectrum of a coumarin dye, and of the infrared spectrum of alanine. We show that with our approach it becomes possible to obtain error bars for calculated spectra that account for uncertainties in the molecular structure. This is an important first step towards systematically quantifying other relevant sources of uncertainty in theoretical spectroscopy.

Graphical abstract: Towards theoretical spectroscopy with error bars: systematic quantification of the structural sensitivity of calculated spectra

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Supplementary files

Article information


Submitted
09 Oct 2019
Accepted
20 Dec 2019
First published
27 Dec 2019

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Towards theoretical spectroscopy with error bars: systematic quantification of the structural sensitivity of calculated spectra

T. G. Bergmann, M. O. Welzel and C. R. Jacob, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC05103A

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