Collision-induced dissociation and theoretical studies of K+ complexes with ammonia: a test of theory for potassium ions

Iceman, Christopher; Armentrout, P. B.

doi:10.1016/s1387-3806(02)00954-5

Cited by 42 publications

(48 citation statements)

References 51 publications

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“…A few theoretical PCAs are available for comparison for NH 3 . [33,37,44,47] The EP(K ) PCA is in good agreement with all the reported values based on calculations with allelectron basis sets. In comparison, the two values reported in ref.…”

Section: Introductionsupporting

confidence: 88%

“…[47] using pseudopotential are too low by over 10 kJ mol À1 . Our EP(K ) PCA is virtually identical to that obtained at the B3-LYP/6-311 G(2d,2p)//B3-LYP/6-311 G(2d,2p) [37] and B3-LYP/6-311 G(2d,2p)//B3-LYP/6-31G(d) levels, [47] and this indicates that if sufficiently large basis sets are used, the effects of geometry and zero-point corrections on K binding affinities would be minimal. Interestingly, for K -(NH 3 ) n complexes (n 1 ± 5), the BSSE at the B3-LYP level is small (within AE 1 kJmol À1 ) when compared to the BSSE obtained by MP2 calculations (3 ± 4 kJmol À1 ) using the same basis set.…”

Section: Introductionmentioning

confidence: 98%

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Absolute Potassium Cation Affinities (PCAs) in the Gas Phase

Lau

Wong

et al. 2003

Chemistry A European J

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The potassium cation affinities (PCAs) of 136 ligands (20 classes) in the gas phase were established by hybrid density functional theory calculations (B3-LYP with the 6-311+G(3df,2p) basis set). For these 136 ligands, 70 experimental values are available for comparison. Except for five specific PCA values-those of phenylalanine, cytosine, guanine, adenine (kinetic-method measurement), and Me(2)SO (by high-pressure mass spectrometric equilibrium measurement)-our theoretical estimates and the experimental affinities are in excellent agreement (mean absolute deviation (MAD) of 4.5 kJ mol(-1)). Comparisons with previously reported theoretical PCAs are also made. The effect of substituents on the modes of binding and the PCAs of unsubstituted parent ligands are discussed. Linear relations between Li+/Na+ and K+ affinities suggest that for the wide range of ligands studied here, the nature of binding between the cations and a given ligand is similar, and this allows the estimation of PCAs from known Li+ and/or Na+ affinities. Furthermore, empirical equations relating the PCAs of ligands with their dipole moments, polarizabilities (or molecular weights), and the number of binding sites were established. Such equations offer a simple method for estimating the PCAs of ligands not included in the present study.

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Section: Introductionsupporting

confidence: 88%

Section: Introductionmentioning

confidence: 98%

Absolute Potassium Cation Affinities (PCAs) in the Gas Phase

Lau

Wong

et al. 2003

Chemistry A European J

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“…Eq. (2) has been shown to accurately describe kinetic shifts in a number of previous CID experiments [38][39][40][41][42][43].…”

Section: Thermochemical Analysismentioning

confidence: 97%

“…The 6-311+G(d,p) basis set used for geometry optimizations is a bit larger than the basis sets used for prior theoretical calculations in our laboratories [38,41]. Previous work in our group has suggested that the use of diffuse functions for the initial optimization is important to better handle hydrogen bonding within K + (L) complexes where L = glycine and complexes that contain functional components of glycine [42].…”

Section: Computational Detailsmentioning

confidence: 99%

“…Previous work in our group [38] on K + (NH 3 ) x complexes has shown that the use of relativistic Hay-Wadt [56] and Stuttgart-Dresden [57] effective core potentials (ECP) for potassium underestimates the metal-ligand binding energies. Because Ca 2+ (H 2 O) x is isoelectronic with K + (NH 3 ) x , pseudopotential calculations were not considered here.…”

Section: Computational Detailsmentioning

confidence: 99%

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Binding energies for the inner hydration shells of Ca2+: An experimental and theoretical investigation of Ca2+(H2O)x complexes (x=5–9)

Carl

Moision

Armentrout

2007

International Journal of Mass Spectrometry

103

136

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Gas‐Phase Cation Affinity and Basicity Scales

Laurence

Gal

2009

Lewis Basicity and Affinity Scales

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The study of the formation of complexes between cations and chemical species in the gas phase offers the unique possibility of measuring the intrinsic (i.e. free of solvent and counter ion influences) Lewis basicity of these species. Although the charge-transfer component of the interaction energy in cation adducts is normally smaller than the electrostatic and polarization components, gas-phase cations are generally considered as archetypal Lewis acids because the full positive charge of the naked cation allows strong binding with classical Lewis bases. In fact, almost any entity bearing some electron density, such as the rare gases, can form complexes with cations that may be observable in the gas phase.There is a large array of cations that have been studied in the gas phase for their interaction with Lewis bases (generally neutral organic molecules) and are still being actively investigated today. The most studied is the proton [1-6]. This special cation will not be dealt with in this chapter (however, see Section 1.3 in Chapter 1), since the proton and its transfer serve to define the Brönsted acids and bases, as opposed to Lewis acids and bases, which do not exchange protons. Moreover, although the proton and a cation with an empty orbital may be seen as identical from the point of view of the Lewis theory, the special 'electronic structure' of the proton (in fact the absence of any electron) makes the proton affinity and basicity scales completely different, qualitatively and quantitatively, from any other cation scales. A significant part of the studies of the interaction of gas-phase metal cations with organic molecules was devoted to their chemical reactivity: bond insertion, bond cleavage, elimination and so on. This aspect is not considered here, although some of these reactions may be used as indirect routes for the formation of cation/molecule adducts.Apart from the proton, experimental studies have focused primarily on the binding of alkali metal cations and transition metal monocations. Few studies have considered alkaline Lewis Basicity and Affinity Scales: Data and Measurement

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Collision-induced dissociation and theoretical studies of K+ complexes with ammonia: a test of theory for potassium ions

Cited by 42 publications

References 51 publications

Absolute Potassium Cation Affinities (PCAs) in the Gas Phase

Absolute Potassium Cation Affinities (PCAs) in the Gas Phase

Binding energies for the inner hydration shells of Ca2+: An experimental and theoretical investigation of Ca2+(H2O)x complexes (x=5–9)

Gas‐Phase Cation Affinity and Basicity Scales

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