An exploration of the ozone dimer potential energy surface

Azofra, Luis Miguel; Alkorta, Ibón; Scheiner, Stefan

doi:10.1063/1.4884962

Cited by 8 publications

(7 citation statements)

References 56 publications

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“…Dissociation energies for the C i and Cs-B inplane structures obtained by Azofra et al [24] and Gadziev et al [25] are much larger than found here. It appears that in both cases BSSE corrections were not applied.…”

Section: Structures and Dissociation Energies For Complexes Of Ozone ...contrasting

confidence: 58%

Ab initio studies on complexes of ozone with triatomic and larger molecules.

Grein

2022

Preprint

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Using coupled cluster methods with quadruple-zeta basis sets stable structures were found for complexes of ozone with common triatomic molecules as well as with ammonia and methane. The largest dissociation energy of 917 cm− 1 was obtained for the hydrogen bonded O3-NH3 complex, exceeding the value for O3-H2O (787 cm− 1). The high dissociation energy of the O3-NH3 complex is seen as an exception to the expected sequence of stabilities. Large dissociation energies were obtained also for O3-SO2 (717 cm− 1), O3-N2O (688 cm− 1), O3-HCN (659 cm− 1) and O3-CO2 (652 cm− 1). Dissociation energies for the C1 structure (559 cm− 1) and Ci structure (556 cm− 1) of the ozone dimer are nearly identical despite pronounced differences in geometries. Hydrogen bonding of HF, H2O, NH3 and CH4 with ozone is contrasted to hydrogen bonding with the oxygen molecule. Large shifts in vibrational frequencies were found for the ozone dimer, with a red shift of 51 cm− 1 and a blue shift of 25 cm− 1 for the antisymmetric stretching band of ozone. Larger frequency shifts are also seen for complexes of ozone with NH3, HCN, H2O and N2O.

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Section: Structures and Dissociation Energies For Complexes Of Ozone ...contrasting

confidence: 58%

Ab initio studies on complexes of ozone with triatomic and larger molecules.

Grein

2022

Preprint

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“…The same sort of tetrel bonding through a C π-hole occurs in other systems as well [ 32 , 33 ]. This idea is not restricted to C but occurs on other sorts of atoms—for example, the S atom of SO 2 [ 31 ] or SO 3 [ 34 ] or the central O of ozone [ 35 ] or for tetrel T atoms larger than C, as in F 2 TO [ 36 , 37 , 38 ], or the N atom of the -NO 2 group [ 39 ]. Other planar examples involve triel (Tr) atoms in TrR 3 , where R indicates some substituent [ 40 , 41 ].…”

Section: Introductionmentioning

confidence: 99%

Versatility of the Cyano Group in Intermolecular Interactions

Scheiner

2020

Molecules

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Several cyano groups are added to an alkane, alkene, and alkyne group so as to construct a Lewis acid molecule with a positive region of electrostatic potential in the area adjoining these substituents. Although each individual cyano group produces only a weak π-hole, when two or more such groups are properly situated, they can pool their π-holes into one much more intense positive region that is located midway between them. A NH3 base is attracted to this site, where it forms a strong noncovalent bond to the Lewis acid, amounting to as much as 13.6 kcal/mol. The precise nature of the bonding varies a bit from one complex to the next but typically contains a tetrel bond to the C atoms of the cyano groups or the C atoms of the linkage connecting the C≡N substituents. The placement of the cyano groups on a cyclic system like cyclopropane or cyclobutane has a mild weakening effect upon the binding. Although F is comparable to C≡N in terms of electron-withdrawing power, the replacement of cyano by F substituents substantially weakens the binding with NH3.

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“…The recent development of the concept of chalcogen bond [29][30][31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] leads naturally to the need to explore the importance of such bonds that involve CO 2 . Also relevant are the recent findings that the C atom can participate in fairly strong noncovalent bonds, commonly referred to as tetrel bonds.…”

Section: Introductionmentioning

confidence: 99%

Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO2

Azofra

Scheiner

2015

The Journal of Chemical Physics

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The complexes formed by H 2 CO, CH 3 CHO, and (CH 3) 2 CO with 1, 2, and 3 molecules of CO 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 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.

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An exploration of the ozone dimer potential energy surface

Cited by 8 publications

References 56 publications

Ab initio studies on complexes of ozone with triatomic and larger molecules.

Ab initio studies on complexes of ozone with triatomic and larger molecules.

Versatility of the Cyano Group in Intermolecular Interactions

Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO2

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