INVESTIGADORES
PETELSKI Andre Nicolai
artículos
Título:
Nature and Strength of Weak O⋅⋅⋅O Interactions in Nitryl Halide Dimers
Autor/es:
PETELSKI, ANDRE NICOLAI; DUARTE, DARÍO JORGE ROBERTO; PERUCHENA, NÉLIDA MARÍA
Revista:
Chemphyschem
Editorial:
WILEY-V C H VERLAG GMBH
Referencias:
Año: 2022
ISSN:
1439-4235
Resumen:
The use of real space functions and molecular graphs has pushed some chemists to wonder: Are interactions between negatively charged oxygen atoms possible? In this contribution we analyze whether there is a real interaction between oxygen atoms in nitryl halide dimers (XNO2)2 (X=F, Cl, Br and I) and in tetranitromethane and derivatives. Based on ab-initio and density functional theories (DFT) methods, we show these complexes are weakly stabilized. Energy decomposition analyses based on local molecular orbitals (LMOEDA) and interacting quantum atoms (IQA) reveal both dispersion and exchange play a crucial role in the stabilization of these complexes. Electron charge density and IQA analyses indicate that the oxygen atoms are connected by privileged exchange channels. In addition, electrostatic interactions between O and N atoms are also vital for the stabilization of the complexes. Finally, a reasonable explanation is given for the dynamic behavior of nitryl groups in tetranitromethane and derivatives.