We introduce density functional theory and review recent progress in its application to transition metal chemistry. Topics covered include local, meta, hybrid, hybrid meta, and range-separated functionals, band theory, software, validation tests, and applications to spin states, magnetic exchange coupling, spectra, structure, reactivity, and catalysis, including molecules, clusters, nanoparticles, surfaces, and solids.

Density functional theory for transition metals and transition metal chemistry

Molybdenum(VI) speciation in sulfidic waters; stability and lability of thiomolybdates

Rhamnogalacturonan-II, a Pectic Polysaccharide in the Walls of Growing Plant Cell, Forms a Dimer That Is Covalently Cross-linked by a Borate Ester IN VITRO CONDITIONS FOR THE FORMATION AND HYDROLYSIS OF THE DIMER

Applications of the method of continuous variations (MCV or the Method of Job) to problems of interest to organometallic chemists are described. MCV provides qualitative and quantitative insights into the stoichiometries underlying association of m molecules of A and n molecules of B to form AmBn . Applications to complex ensembles probe associations that form metal clusters and aggregates. Job plots in which reaction rates are monitored provide relative stoichiometries in rate-limiting transition structures. In a specialized variant, ligand- or solvent-dependent reaction rates are dissected into contributions in both the ground states and transition states, which affords insights into the full reaction coordinate from a single Job plot. Gaps in the literature are identified and critiqued.

/pdf/method-of-continuous-variations-applications-of-job-plots-to-3nx4ynwsfs.pdf

Method of Continuous Variations: Applications of Job Plots to the Study of Molecular Associations in Organometallic Chemistry[**]

Carbohydrates as ligands: coordination equilibria and structure of the metal complexes

In this paper, the authors recall and systemize the restrictions to the application of Job's method, illustrate its use associated to proton magnetic resonance spectral intensities, and present some results of a computer program they developed for the case of multiple equilibria.

On the use of the method of continuous variations

The nature and types of lone-pair effects on nuclear spin coupling constants are reviewed in the context of a localized bond description of molecular electronic structure. Emphasis is placed on the importance of residual delocalization involving the otherwise lone-pair orbital, in terms of which the effect of an X lone-pair, when compared with an isoelectronic YH or XH+ group or with an XR group, and its orientational dependence can be interpreted. One-, two- and three-bond coupling constants are considered and the importance of lone-pair effects for configurational and conformational information is stressed and illustrated. They also serve for a better understanding of substituent inductive effects on coupling constants.



A large collection of illustrative examples are presented, with particular attention paid to couplings involving H, C, N, F and P nuclei, organized in a systematic manner into nine categories. The signs of the lone-pair effects on the reduced coupling constants are found to be independent of the actual nuclei under study in the same category. This is taken as an indication that the electron lone-pairs mainly affect the Fermi contact contribution to the coupling and, accordingly, an interpretation is given in terms of simple sum-over-states models. In addition, symmetry-based relationships are established involving the sign of lone-pair effects in coupling constants between nuclei which are a different number of bonds apart.

Effect of electron lone-pairs on nuclear spin–spin coupling constants

The problem of a relativistic spin 1/2 particle confined to a one-dimensional box is solved in a way that resembles closely the solution of the well known quantum-mechanical textbook problem of a non-relativistic particle in a box. The energy levels and probability density are computed and compared with the non-relativistic case. Resumo. O problema de uma particula de spin 1/2 confinada por uma caixa a uma dimensao e resolvido de uma maneira muito semelhante a da resolucao do problema de uma particula no-relativista numa caixa referido em muitos livros introdutorios de Mecânica Quntâica. Os niveis de energia e a densidade de probabilidade sao calculados e comparados com os valores nao-relativistas.

/pdf/relativistic-particle-in-a-box-a9234vpg6v.pdf

Victor M. S. Gil

Papers

On the use of the method of continuous variations

Effect of electron lone-pairs on nuclear spin–spin coupling constants

Relativistic particle in a box

The Complexity of Teaching and Learning Chemical Equilibrium

NMR spectroscopy study of the complexation of d-gluconic acid with tungsten(VI) and molybdenum(VI)