Complexes containing CO2 and SO2. Mixed dimers, trimers and tetramers

Literature Information

Publication Date 2014-01-27
DOI 10.1039/C3CP55489A
Impact Factor 3.676
Authors

Steve Scheiner


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Abstract

Mixed dimers, trimers and tetramers composed of SO2 and CO2 molecules are examined by ab initio calculations to identify all minimum energy structures. While AIM formalism leads to the idea of a pair of C⋯O bonds in the most stable heterodimer, bound by some 2 kcal mol−1, NBO analysis describes the bonding in terms of charge transfer from O lone pairs of SO2 to the CO π* antibonding orbitals. The second minimum on the surface, just slightly less stable, is described by AIM as containing a single O⋯O chalcogen bond. The NBO picture is that of two transfers in opposite directions: one from a SO2 O lone pair to a π* antibond of CO2, supplemented by CO2 Olp → π*(SO). Decomposition of the interaction energies points to electrostatic attraction and dispersion as the dominant attractive components, in roughly equal measure. The various heterotrimers and tetramers generally retain the dimer structure as a starting point. Cyclic oligomers are favored over linear geometries, with a preference for complexes containing larger numbers of SO2 molecules.

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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