Ab initio study of the stepwise hydration of NO+

doi:10.1016/0009-2614(84)85681-X

Chemical Physics Letters

Volume 107, Issue 2, 25 May 1984, Pages 107-111

https://doi.org/10.1016/0009-2614(84)85681-X Get rights and content

Abstract

The structure of NO⁺-H₂O is determined by ab initio calculations, in an extended polarized basis set supplemented by the dispersion energy, to be an angular adduct. The hydration energy of 21.92 kcal/mole compares well with the experimental value corrected for zero-point energy. The structure of the successive hydrates up to n = 4 are studied in an appropriate smaller basis and provide an explanation for the ease of formation of HNO₂ and H₃O⁺ in the atmosphere at the tetrahydrate level.

References (28)

K. Hirao et al.
Chem. Phys. Letters
(1982)
A. Pullman et al.
Chem. Phys. Letters
(1981)
R.S. Narcisi et al.
J. Geophys. Res.
(1965)
E.E. Ferguson et al.
Accounts Chem. Res.
(1981)
F.C. Fehsenfeld et al.
J. Geophys. Res.
(1969)
E.E. Ferguson et al.
J. Geophys. Res.
(1969)
F.C. Fehsenfeld et al.
J. Chem. Phys.
(1971)
M.A. French et al.
Can. J. Chem.
(1973)
H. Berthod et al.
Israel J. Chem.
(1980)
A. Pullman, in: Chemical events in the atmospere, ed. E. Marino-Bettolo (Pontifical Academy of Sciences), to be...

B. Pullman et al.

Theoret. Chim. Acta

(1977)

W. Kolos

Theoret. Chim. Acta

(1980)

A. Pullman et al.

Intern. J. Quantum Chem.

(1976)

Cited by (19)

Calculated thermodynamics of reactions involving NO+· X complexes ( where X = H<inf>2</inf>O, N<inf>2</inf> and CO<inf>2</inf>)
1997, Chemical Physics
Ab initio calculations using Møller-Plesset perturbation theory to the second and fourth orders have been performed on the NO⁺·X complexes (X = H₂O, N₂ and CO₂). Optimised geometries (giving rotational constants) and vibrational frequencies as well as computed total energies have been used to calculate enthalpies, entropies and Gibbs free energies for the complexing reactions and ligand-switching reactions between the three molecular complexes. The results obtained have been compared with experimental values, where available. Although ab initio molecular orbital calculations have previously been performed on these NO⁺ complexes, minimum energy structures for X = N₂ and CO₂ have only been determined using methods which did not include electron correlation and there has been no study in which all three complexes were examined using the same computational method. In this work, a relatively cost-effective computational approach has been developed which allows reliable thermodynamic quantities associated with all three complexes to be calculated. The following thermodynamic values are recommended for the association reaction NO⁺ + X → NO⁺·X: ΔH₂₉₈ = −18.3, −4.6 and −8.8 kcal mol⁻¹ and ΔS₂₉₈ = −23.6, −19.6 and −20.2 cal mol⁻¹ K⁻¹, for X = H₂O, N₂ and CO₂, respectively. Also, for the first time, standard enthalpy and entropy changes are presented for ligand-switching reactions involving these complexes. Of note is that for the association reaction with X = N₂, ΔG is positive at 298 K, but at temperatures typical of the ionosphere, ΔG is negative. The implications of the computed quantities to ionospheric chemistry and ion mobility mass spectrometric studies are briefly discussed. The structures of the complexes are viewed in terms of Lewis acid/base behaviour.
Classical path calculations of the vibrational relaxation of O+<inf>2</inf> in collisions with He and near thermal energies
1993, International Journal of Mass Spectrometry and Ion Processes
The vibrational relaxation rate constants for the recent measurements in the Innsbruck laboratory of the vibrational transitions 1 → 0 and 2 → 1 in the O⁺₂He collision system were calculated using the semiclassical (classical path) method developed by Billing [G.D. Billing, J. Chem. Phys., 61 (1974) 3340; Chem. Phys., 9 (1975) 359; Computer Phys. Rept., 1 (1984) 237]. The global 3D potential energy surface for dynamics calculations was constructed, using plausible additional assumptions, on the basis of the procedure proposed by Gislason and Ferguson [E.A. Gislason and E.E. Ferguson, J. Chem. Phys., 87 (1987) 6474] to estimate the local (equilibrium geometry) properties of the O⁺₂—M and NO⁺—M collision complexes. The good agreement between theoretical and experimental data, achieved in the collision energy range from thermal energies up to ≈0.35 eV, provides strong support to the postulates of the method of Gislason and Ferguson. The possibilities to further refine our procedure for construction of global 3D interaction potentials and to extend it to other classes of collision systems are also discussed.
Flow Tube Studies of Ion-Molecule Reactions
1989, Advances in Atomic and Molecular Physics
This chapter focuses on the advancements in the ion–molecule interaction processes during the past several years of measurements. The chapter considers a few aspects of charge-transfer processes, some chemical reactions, and the recent vibrational energy transfer investigations leading to useful generalities and insights into ion neutral interaction mechanisms. Flow tubes do not play the dominant role in the area of reaction mechanistic studies that they have in their aeronomical and astrophysical applications by virtue of their chemical versatility. Thermal energy ion–molecule reactions have a strong propensity to proceed efficiently along the lowest energy pathways between reactants and products, without steric or Franck–Condon, or sometimes even spin conservation restraints. The negative temperature dependences of charge-transfer and thermal energy ion–atom interchange reactions are invariably weaker than either the experimental temperature dependences of lifetimes deduced from three-body association rate constants or theoretical lifetimes deduced from statistical theories.
Ab-initio calculations relevant to the mechanism of chemical carcinogenesis by N-nitrosamines. Part IV. Decomposition of the α-hydroxynitrosamine
1986, Journal of Molecular Structure: THEOCHEM
An ab initio study of the formation and structure of NO+-(N<inf>2</inf>)<inf>n</inf> (n = 1 and 2) clusters
1985, Chemical Physics Letters
The geometries and clustering energies of the NO⁺ (N₂)_n (n = 1 and 2) clusters have been determined by ab initio calculations at different levels. At the MP4SDQ/6-31G^* level, plus zero-point vibrational corrections making use of the HF/4-31G-optimized geometries, the energy differences between clusters and their relative fragments have been calculated to be −5.3 and −4.1 kcal/mol for n = 1 and n = 2, respectively. These values can be compared to the experimental enthalpies of clustering of −4.4 and −3.9 kcal/mol. The interaction between NO⁺ and N₂ and the structures of two stable cluster ions have also been examined.
On the binding of water to the ammonium ion: The interplay of an improved basis set. Dispersion and zero-point energy
1985, Chemical Physics Letters

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Chemical Physics Letters

Abstract

References (28)

Chem. Phys. Letters

Chem. Phys. Letters

J. Geophys. Res.

Accounts Chem. Res.

J. Geophys. Res.

J. Geophys. Res.

J. Chem. Phys.

Can. J. Chem.

Israel J. Chem.

Theoret. Chim. Acta

Theoret. Chim. Acta

Intern. J. Quantum Chem.

Cited by (19)

Calculated thermodynamics of reactions involving NO<sup>+</sup>· X complexes ( where X = H<inf>2</inf>O, N<inf>2</inf> and CO<inf>2</inf>)

Classical path calculations of the vibrational relaxation of O<sup>+</sup><inf>2</inf> in collisions with He and near thermal energies

Flow Tube Studies of Ion-Molecule Reactions

Ab-initio calculations relevant to the mechanism of chemical carcinogenesis by N-nitrosamines. Part IV. Decomposition of the α-hydroxynitrosamine

An ab initio study of the formation and structure of NO<sup>+</sup>-(N<inf>2</inf>)<inf>n</inf> (n = 1 and 2) clusters

On the binding of water to the ammonium ion: The interplay of an improved basis set. Dispersion and zero-point energy