Density functional theory coordination chemistry

A review of the Journal of Physical Chemistry A, volume 110, issues 6 and 7, reveals that computational chemistry plays a major or supporting role in the majority of papers. Computational tools include use of large Gaussian basis sets and density functional theory, molecular mechanics, and molecular dynamics. There were quantum chemistry studies of complex reaction schemes to create detailed reaction potential energy surfaces/maps, molecular mechanics and molecular dynamics studies of larger chemical systems, and conformational analysis studies. Spectroscopic methods included photoelectron spectroscopy, microwave spectroscopy circular dichroism, IR, UV-vis, EPR, ENDOR, and ENDOR induced EPR. The kinetics papers focused on elucidation of complex mechanisms and potential energy reaction coordinate surfaces. 

Note that the various T and V terms defined in Eqs. (8.3)—(8.5) are functions of the density, while the density itself is a function of three-dimensional spatial coordinates. A function whose argument is also a function is called a functional , and thus the T and V terms are density functionals . The Thomas-Fermi equations, together with an assumed variational principle, represented the first effort to define a density functional theory (DFT) the energy is computed with no reference to a wave function. However, while these equations are of significant historical interest, the underlying assumptions are sufficiently inaccurate that they find no use in modem chemistry (in Thomas-Fermi DFT, all molecules are unstable relative to dissociation into their constituent atoms...)... 

The coordination chemistry of the aminotroponiminates has been reviewed.139 A homoleptic aminotroponiminate complex of yttrium has been prepared and studied by X-ray crystallography and density functional theory calculations.140... 

Chizallet, C., Costentin, G, Che, M., Delbecq, F. and SauteL P. (2006), Revisiting acido-basicity on the MgO surface by periodic density functional theory calculations Role of surface topology and ion coordination on water dissodation. Journal of Physical Chemistry B, 110,15878-86. 

J.A. McCleverty and T.J. Meyer, eds (2004) Comprehensive Coordination Chemistry II, Elsevier, Oxford Volume 2 contains a section Theoretical Models, Computational Methods, and Simulation consisting of a series of articles covering computational methods including molecular mechanics, semi-empirical SCF MO methods, and density functional theory. 

The time-dependent theory of spectroscopy bridges this gap. This approach has received less attention than the traditional time-independent view of spectroscopy, but since 1980, it has been very successfully applied to the field of coordination chemistry.The intrinsic time dependence of external perturbations, for example oscillating laser fields used in electronic spectroscopy, is also expKdtly treated by modern computational methods such as time-dependent density functional theory, a promising approach to the efficient calculation of electronic spectra and exdted-state structures not based on adjustable parameters, as described in Chapter 2.40. In contrast, the time-dependent theory of spectroscopy outlined in the following often relies on parameters obtained by adjusting a calculated spectrum to the experimental data. It provides a unified approach for several spectroscopic techniques and leads to intuitive physical pictures often qualitatively related to classical dynamics. The concepts at its core, time-dependent wave functions (wave packets) and autocorrelation functions, can be measured with femtosecond (fs) techniques, which often illustrate concepts very similar to those presented in the following for the analysis of steady-state spectra. The time-dependent approach therefore unifies spectroscopic... 

Neese, F. (2009). Prediction of molecular properties and molecular spectroscopy with density functional theory From fundamental theory to exchange-coupling. Coordination Chemistry Reviews, 253, 526-563. 

Autschbach, J. (2007). Density functional theory applied to calculating optical and spectroscopic properties of metal complexes NMR and optical activity. Coordination Chemistry Reviews, 251,... 

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