1. The first microsolvation step for furans: New experiments and benchmarking strategies
- Author
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Melanie Schnell, Majdi Hochlaf, Leonardo Baptista, Dzmitry S. Firaha, Giovanni Bistoni, Jens Antony, Hannes C. Gottschalk, David M. Benoit, Kai Leonhard, Leif C. Kröger, Fabian Bohle, Frank Neese, Muthuramalingam Prakash, Alexander A. Auer, Andreas Hansen, Inga S. Ulusoy, Stefan Grimme, Max N. Pereira, Michael E. Harding, Wassja A. Kopp, Christof Holzer, Daniel A. Obenchain, Anja Poblotzki, Georg Jansen, Muneerah Mogren Al-Mogren, Małgorzata Krasowska, Ricardo A. Mata, Martin A. Suhm, Cristobal Perez, Wim Klopper, Mariyam Fatima, Halima Mouhib, Rahma Dahmani, Institut für Physikalische Chemie [Göttingen], Georg-August-University [Göttingen], Deutsches Elektronen-Synchrotron [Hamburg] (DESY), Mulliken Center for Theoretical Chemistry, Universität Bonn, parent, Max Planck Institute for Chemical Energy Conversion, Max-Planck-Gesellschaft, Universidade Federal do Estado do Rio de Janeiro (UNIRIO), University of Hull [United Kingdom], University of Bonn, Laboratoire Instrumentation, Simulation et Informatique Scientifique (COSYS-LISIS), Université Gustave Eiffel, RWTH Aachen University, Institute of Nanotechnology [Karlsruhe] (INT), Karlsruhe Institute of Technology (KIT), Karlsruher Institut für Technologie (KIT), Universität Duisburg-Essen [Essen], King Saud University [Riyadh] (KSU), SRM Institute of Science and Technology (SRM), and Heidelberg University
- Subjects
Technology ,Infrared ,PREDICTION ,Chemie ,Ab initio ,General Physics and Astronomy ,Electronic structure ,010402 general chemistry ,INTERNAL-ROTATION SPLITTINGS ,01 natural sciences ,DENSITY-FUNCTIONAL THEORY ,Quantum state ,0103 physical sciences ,MICROWAVE SPECTROSCOPY ,WATER ,ddc:530 ,Physical and Theoretical Chemistry ,Physics::Chemical Physics ,Wave function ,Astrophysics::Galaxy Astrophysics ,Physics ,AB-INITIO ,010304 chemical physics ,Anharmonicity ,CENTER-DOT-PI ,0104 chemical sciences ,Chemical physics ,GENERAL PROGRAM ,Density functional theory ,Rotational spectroscopy ,[PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph] ,ADAPTED PERTURBATION-THEORY ,ddc:600 ,WAVE-FUNCTION - Abstract
The journal of chemical physics 152(16), 164303 (2020). doi:10.1063/5.0004465, The site-specific first microsolvation step of furan and some of its derivatives with methanol is explored to benchmark the ability of quantum-chemical methods to describe the structure, energetics, and vibrational spectrum at low temperature. Infrared and microwave spectra in supersonic jet expansions are used to quantify the docking preference and some relevant quantum states of the model complexes. Microwave spectroscopy strictly rules out in-plane docking of methanol as opposed to the top coordination of the aromatic ring. Contrasting comparison strategies, which emphasize either the experimental or the theoretical input, are explored. Within the harmonic approximation, only a few composite computational approaches are able to achieve a satisfactory performance. Deuteration experiments suggest that the harmonic treatment itself is largely justified for the zero-point energy, likely and by design due to the systematic cancellation of important anharmonic contributions between the docking variants. Therefore, discrepancies between experiment and theory for the isomer abundance are tentatively assigned to electronic structure deficiencies, but uncertainties remain on the nuclear dynamics side. Attempts to include anharmonic contributions indicate that for systems of this size, a uniform treatment of anharmonicity with systematically improved performance is not yet in sight., Published by American Institute of Physics, Melville, NY
- Published
- 2020
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