Hydrogen atom electron affinity

Two general quantum mechanical procedures were applied to the calculation of atomic electron affinities prior to 1960. These were the variational method and Hartree Fock semi-empirical method. Prior to 1960 there were no accurate calculations for elements other than hydrogen. Indeed, only the electron affinities of C and... 

The hydrogen atom, like the alkali metals (ns ) and halogens (ns np ), has an affinity for the electron and heat is evolved in the following process ... 

Hydrogen bonds are formed to some extent by oxygen ((H20)x, ice, etc.) and perhaps also in some cases by nitrogen. The electrostatic structure for the hydrogen bond explains the observation that only these atoms of high electron affinity form such bonds, a fact for which no explanation was given by the older conception. It is of interest that there is considerable... 

A novel form of Y HX hydrogen bonding49 results when the Lewis base Y is itself a hydride ion (H-). Because the electron affinity of a hydrogen atom is extremely weak (21 kcal mol-1), the H- ion is among the most weakly bound and diffuse anionic species known, and hence a powerful Lewis base. In this case, the H - -HX complex can be referred to as a dihydrogen bond 50 to denote the unusual H-bonding between hydrogen atoms. A water complex of this type was... 

Electron Affinity of Hydrogen, Deuterium, and Tritium Atoms Obtained with 300 Explicitly Correlated Gaussian Functions ... 

Ervin et al. [27] have determined the electron affinity of the acetylide radical, HC = C-, to be equal to 2.969 + 0.010 eV and the enthalpy of the acid dissociation of acetylene in the gas phase to be equal to 377.8 + 0.6 Kcal mol Use these data, together with the ionization potential of the hydrogen atom, 13.595 eV, to calculate the enthalpy for the dissociation of the CH bond in acetylene. The ionization potentials are properly applied at 0 K, but a good approximation is to assume that they are equal to enthalpy changes at 298.15 K, the temperature at which the enthalpy of the acid dissociation was measured. 

Table 1. Atomization energies and electron affinities (kcal/mol) for LiH at QCISD/MG3 geometries for methods that do not involve diffuse functions on hydrogen.

For hydrogen, a = 0.686 is appropriate for a partially negative atom, like that of ethane, 11.7 me, and reproduces its electron affinity. 

The polar effect was at first invoked to explain various directive effects observed in aliphatic systems. Methyl radicals attack propionic acid preferentially at the a-position, ka/kp = 7.8 (per hydrogen), whereas chlorine " prefers to attack at the /3-position, ka/kp = 0.03 (per hydrogen). In an investigation of f-butyl derivatives, a semiquanti-tative relationship was observed between the relative reactivity and the polar effect of the substituents, as evidenced by the pK, of the corresponding acid. In the case of meta- and / ara-substituted toluenes, it has been observed that a very small directive effect exists for some atoms or radicals. When treated by the Hammett relation it is observed that p = —0.1 for H , CeHs , P-CH3C6H4 and CHs . On the contrary, numerous radicals with an appreciable electron affinity show a pronounced polar effect in the reaction with the toluenes. Compilation of Hammett reaction constants and the type of substituent... 

A very useful thermodynamic cycle links three important physical properties homolytic bond dissociation energies (BDE), electron affinities (EA), and acidities. It has been used in the gas phase and solution to determine, sometimes with high accuracy, carbon acidities (Scheme 3.6). " For example, the BDE of methane has been established as 104.9 0.1 kcahmol " " and the EA of the methyl radical, 1.8 0.7 kcal/mol, has been determined with high accuracy by photoelectron spectroscopy (PES) on the methyl anion (i.e., electron binding energy measurements). Of course, the ionization potential of the hydrogen atom is well established, 313.6 kcal/ mol, and as a result, a gas-phase acidity (A//acid) of 416.7 0.7 kcal/mol has been... 

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