Electron affinity transition metal atoms

Electron affinities and ionization potentials of Ad and 5d transition metal atoms by CCSD(T), MP2 and density functional theory ... 

Balabanov, N.B., Peterson, K.A. Basis set limit electronic excitation energies, ionization potentials, and electron affinities for the 3d transition metal atoms Coupled cluster and multireference methods, J. Chem. Phys. 2006,125,074110. 

TABLE 4.18 Synopsis for the Structural Parameters Employed in this Work for the Second, Third and Fourth Period Transitional Metals Atomic Number (Z), Atomic Mass (A), Atomic Radius (R), Melting Point (MP), Boiling Point (BP), Density (p) (Horovitz et al., 2000), Finite Difference Electronegativity (x-FD) and Chemical Hardness (rj-FD), Experimental Ionization Potential (EXP-IP) and Electronic Affinity (EXP-EA) (Putz, 2008a), and Their Density Functional Theory Third Order (DFT[3]) Counterpart (Putz, 2006)... 

N. B. Balabanov and K. A. Peterson,/. Chem. Phys., 125, 074110 1-10 (2006). Basis Set Limit Electronic Excitation Energies, Ionization Potentials, and Electron Affinities for the 3d Transition Metal Atoms Coupled Cluster and Multireference Methods. 

In 1994, we began our first calculations on the electron affinities of the rare earths [8], These are the most difficult atoms to treat, due to the open /-subshells, followed by the transition metal atoms with their open ri-subshells. At that time, some accelerator mass spectrometry (AMS) measurements of the lanthanides existed [9,10] which were rough. Larger values might be due to multiple bound states, states were uncharacterized as to dominant configuration, etc. 

The alkaline and rare-earth metals, and positive actinide ions, generally have greater affinity for —0 groups as electron donors. Many transition metals complex preferentially with enoHc —0 and some nitrogen functions. PolarizabiUty of the donor atoms correlates with stabiUty of complexes of the heavier transition metals and the more noble metal ions. 

A measure of the Lewis acidity of a metal ion is determined by its affinity for a pair of electrons, and the greater this affinity, the more stable the complexes formed by the metal ion will be. However, removing electrons from a metal to produce an ion is also related to the attraction the metal atom has for electrons. Therefore, it seems reasonable to seek a correlation between the stability constants for complexes of several metals with a given ligand and the total energy necessary for ionization to produce the metal ions. The first-row transition metal ions react in solution with ethylenediamine, en, to form stable complexes. We will consider only the first two steps in complex formation, which can be shown as follows ... 

The importance of scalar relativistic effects for compounds of transition metals and/or heavy main group elements is well established by now [44], Somewhat surprisingly (at first sight), they may have nontrivial contributions to the TAE of first-row and second-row systems as well, in particular if several polar bonds to a group VI or VII element are involved. For instance, in BF3, S03) and SiF4, scalar relativistic effects reduce TAE by 0.7, 1.2, and 1.9kcal/mol, respectively - quantities which clearly matter even if only chemical accuracy is sought. Likewise, in a benchmark study on the electron affinities of the first-and second-row atoms [45] - where we were able to reproduce the experimental values to... 

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