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Título
How accurate is the determination of equilibrium structures for van der Waals complexes? The dimer N2O⋯CO as an example
Autor
Año del Documento
2021
Editorial
AIP Publishing
Descripción
Producción Científica
Documento Fuente
The Journal of Chemical Physics, 2021, vol. 154, n. 19. 12 p.
Abstract
Plausible methods for accurate determination of equilibrium structures of intermolecular clusters have been assessed for the van der Waals dimer N2O⋯CO. In order to assure a large initial dataset of rotational parameters, we first measured the microwave spectra of the 15N2O⋯12CO and 15N2O⋯13CO isotopologs, expanding previous measurements. Then, an anharmonic force field was calculated ab initio and a semi-experimental equilibrium structure was determined. The dimer structure was also calculated at the coupled-cluster level of theory using very large basis sets with diffuse functions and counterpoise correction. It was found that the contributions of the diffuse functions and the counterpoise correction are not additive and do not compensate each other although they have almost the same value but opposite signs. The semi-experimental and ab initio structures were found to be in fair agreement, with the equilibrium distance between the centers of mass of both monomers being 3.825(13) Å and the intermolecular bond length r(C⋯O) = 3.300(9) Å. In this case, the mass-dependent method did not permit us to determine reliable intermolecular parameters. The combination of experimental rotational constants and results of ab initio calculations thus proves to be very sensitive to examine the accuracy of structural determinations in intermolecular clusters, offering insight into other aggregates.
Palabras Clave
Intermolecular forces
Fuerzas intermoleculares
Ab-initio methods
Métodos ab initio
ISSN
1089-7690
Revisión por pares
SI
Patrocinador
Ministerio de Ciencia e Innovación - Fondo Europeo de Desarrollo Regional (grant PGC2018-098561-B-C22)
Version del Editor
Propietario de los Derechos
© 2021 AIP Publishing
Idioma
eng
Tipo de versión
info:eu-repo/semantics/acceptedVersion
Derechos
openAccess
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