The proton affinities of the halogen acids

Polley, Charles W.; Munson, Burnaby

doi:10.1016/0020-7381(78)80004-7

Cited by 20 publications

(2 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[55] For the c‐C 3 H 2 ···HF complex, the proton is mostly localized toward the heavy atom F, which results in a single, steep potential well, and thus the magnitude of stretching the HF bond is the smallest, and that of the HBr bond the largest. These findings are consistent with the larger proton affinity of the smaller halides,[56] which is also reflected in the lengthening of the HX bond length on complexation (0.035 Å for HF, 0.054 Å for HCl and 0.076 Å for HBr).…”

Section: Resultssupporting

confidence: 86%

An electronic structure theory investigation of the physical chemistry of the intermolecular complexes of cyclopropenylidene with hydrogen halides

Varadwaj

Peslherbe

2012

J Comput Chem

View full text Add to dashboard Cite

The proton accepting and donating abilities of cyclopropenylidene (c-C(3)H(2)) on its complexation with hydrogen halides H-X (X = F, Cl, Br) are analyzed using density-functional theory with three functionals (PBE0, B3LYP, and B3LYP-D) and benchmarked against second-order Møller-Plesset (MP2) theory. Standard signatures including, inter alia, dipole moment enhancement, charge transfer from the carbenic lone pair to the antibonding σ*(H-X) orbital, and H-X bond elongation are examined to ascertain the presence of hydrogen bonding in these complexes. The latter property is found to be accompanied with a pronounced red shift in the bond stretching frequency and with a substantial increase in the infrared intensity of the band on complex formation. The MP2/aug-cc-pVTZ c-C(3)H(2)···H-F complex potential energy surface turns out to be an asymmetric deep single well, while asymmetric double wells are found for the c-C(3)H(2)···H-Cl and c-C(3)H(2)···H-Br complexes, with an energy barrier of 4.1 kcal mol(-1) for proton transfer along the hydrogen bond in the latter complex. Hydrogen-bond energy decomposition, with the reduced variational space self-consistent field approach, indicates that there are large polarization and charge-transfer interactions between the interacting partners in c-C(3)H(2)···H-Br compared to the other two complexes. The C···H bonds are found to be predominantly ionic with partial covalent character, unveiled by the quantum theory of atoms in molecules. The present results reveal that the c-C(3)H(2) carbene divalent carbon can act as a proton acceptor and is responsible for the formation of hydrogen bonds in the complexes investigated.

show abstract

Section: Resultssupporting

confidence: 86%

An electronic structure theory investigation of the physical chemistry of the intermolecular complexes of cyclopropenylidene with hydrogen halides

Varadwaj

Peslherbe

2012

J Comput Chem

View full text Add to dashboard Cite

show abstract

“…Reasons have already been given in the current paper as to why an initially formed [Cl 3 O 2 ] + complex does not form [O 2 ] + and both Cl and Cl 2 . Fluoronium salts are much less stable than their chloronium counterparts, such as shown by the relative proton affinities of HF and HCl [116][117][118][119][120] A careful look at our diverse reaction mechanisms shows that they all are examples of the general inorganic chemical reaction…”

Section: Discussionmentioning

confidence: 99%

Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides

2020

View full text Add to dashboard Cite

In this review, we discuss different ions of oxygen and fluorine and related oxyfluorides and isoelectronic species from the viewpoint of their potential ambisaline character, defined as a property of species X so that both X + and X − may both be found in isolable salts. The term is applied to the ions as well as to the neutral precursor. Reactivity versus stability, reported and plausible synthetic approaches of well-established and probable species are discussed from the perspective of thermochemistry.

show abstract

Molecular Beam Photoionization Studies of Molecules and Clusters

1982

Advances in Chemical Physics

View full text Add to dashboard Cite

The proton affinities of the halogen acids

Cited by 20 publications

References 19 publications

An electronic structure theory investigation of the physical chemistry of the intermolecular complexes of cyclopropenylidene with hydrogen halides

An electronic structure theory investigation of the physical chemistry of the intermolecular complexes of cyclopropenylidene with hydrogen halides

Paradoxes and paradigms: on ambisaline ions of oxygen, fluorine, and related oxyfluorides

Molecular Beam Photoionization Studies of Molecules and Clusters

Contact Info

Product

Resources

About