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

Physical Chemistry Chemical Physics, vol. 25, pp. 7688–7696

Abstract

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.

Authors 5

1. Lilian W. Sutikdja Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074, Aachen, Germany

2. Ha Vinh Lam Nguyen corresponding

   Centre National de la Recherche Scientifique · Institut Universitaire de France · Université Paris-Est Créteil · Université Paris Cité · Laboratoire Interuniversitaire des Systèmes Atmosphériques

   Affiliation as printed

   Institut Universitaire de France (IUF), F-75231, Paris cedex 05, France

   Univ Paris Est Creteil and Université Paris Cité, CNRS, LISA, F-94010, Créteil, France

3. Dragan Jelisavac Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074, Aachen, Germany

4. Wolfgang Stahl Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, D-52074, Aachen, Germany

5. Halima Mouhib corresponding

   Vrije Universiteit Amsterdam

   Affiliation as printed

   Department of Computer Science, VU Bioinformatics, Vrije Universiteit Amsterdam, De Boelelaan 1111, 1081 HV, Amsterdam, The Netherlands