Issue 11, 2023

Benchmarking quantum chemical methods for accurate gas-phase structure predictions of carbonyl compounds: the case of ethyl butyrate

Abstract

High-resolution spectroscopy techniques play a pivotal role to validate and efficiently benchmark available methods from quantum chemistry. In this work, we analyzed the microwave spectrum of ethyl butyrate within the scope of a systematic investigation to benchmark state-of-the-art exchange–correlation functionals and ab initio methods, to accurately predict the lowest energy conformers of carbonyl compounds in their isolated state. Under experimental conditions, we observed two distinct conformers, one of Cs and one of C1 symmetry. As reported earlier in the cases of some ethyl and methyl alkynoates, structural optimizations of the most abundant conformer that exhibits a C1 symmetry proved extremely challenging for several quantum chemical levels. To probe the sensitivity of different methods and basis sets, we use the identified soft-degree of freedom in proximity to the carbonyl group as an order parameter. The results of our study provide useful insight for spectroscopists to select an adapted method for structure prediction of carbonyl compounds based on their available computational resources, suggesting a reasonable trade-off between accuracy and CPU cost. At the same time, our observations and the resulting sets of highly accurate experimental constants from high-resolution spectroscopy experiments give an appeal to theoretical groups to look further into this seemingly simple family of chemical compounds, which may prove useful for the further development and parametrization of theoretical methods in computational chemistry.

Graphical abstract: Benchmarking quantum chemical methods for accurate gas-phase structure predictions of carbonyl compounds: the case of ethyl butyrate

Supplementary files

Article information

Article type
Paper
Submitted
10 12 2022
Accepted
07 2 2023
First published
09 2 2023
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2023,25, 7688-7696

Benchmarking quantum chemical methods for accurate gas-phase structure predictions of carbonyl compounds: the case of ethyl butyrate

L. W. Sutikdja, H. V. L. Nguyen, D. Jelisavac, W. Stahl and H. Mouhib, Phys. Chem. Chem. Phys., 2023, 25, 7688 DOI: 10.1039/D2CP05774C

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