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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}

Abstract

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

Citation Formats

Azofra, Luis M., and Scheiner, Steve, E-mail: steve.scheiner@usu.edu. Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}. United States: N. p., 2015. Web. doi:10.1063/1.4905899.
Azofra, Luis M., & Scheiner, Steve, E-mail: steve.scheiner@usu.edu. Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}. United States. doi:10.1063/1.4905899.
Azofra, Luis M., and Scheiner, Steve, E-mail: steve.scheiner@usu.edu. Wed . "Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}". United States. doi:10.1063/1.4905899.
@article{osti_22416014,
title = {Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}},
author = {Azofra, Luis M. and Scheiner, Steve, E-mail: steve.scheiner@usu.edu},
abstractNote = {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.},
doi = {10.1063/1.4905899},
journal = {Journal of Chemical Physics},
number = 3,
volume = 142,
place = {United States},
year = {Wed Jan 21 00:00:00 EST 2015},
month = {Wed Jan 21 00:00:00 EST 2015}
}