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Title: Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}

The complexes formed by H{sub 2}CO, CH{sub 3}CHO, and (CH{sub 3}){sub 2}CO with 1, 2, and 3 molecules of CO{sub 2} are studied by ab initio calculations. Three different types of heterodimers are observed, most containing a tetrel bond to the C atom of CO{sub 2}, and some supplemented by a CH⋅⋅O H-bond. One type of heterodimer is stabilized by an anti-parallel arrangement of the C=O bonds of the two molecules. The binding energies are enhanced by methyl substitution on the carbonyl, and vary between 2.4 and 3.5 kcal/mol. Natural bond orbital analysis identifies a prime source of interaction as charge transfer into the π*(CO) antibonding orbital. Heterotrimers and tetramers carry over many of the geometrical and bonding features of the binary complexes, but also introduce O⋅⋅O chalcogen bonds. These larger complexes exhibit only small amounts of cooperativity.
Authors:
 [1] ;  [2]
  1. Instituto de Química Médica, CSIC, Juan de la Cierva, 3, E-28006 Madrid (Spain)
  2. Department of Chemistry and Biochemistry, Utah State University, Logan, Utah 84322-0300 (United States)
Publication Date:
OSTI Identifier:
22416014
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 3; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; BINDING ENERGY; CARBON DIOXIDE; CARBON MONOXIDE; CARBONYL RADICALS; CARBONYLS; CHEMICAL BONDS; MOLECULES