Electronic Structure and Spectroscopy

J Li, L Noodleman, DA Case. Electronic structure calculations Density functional methods with applications to transition metal complexes. In EIS Lever, ABP Lever, eds. Inorganic Electronic Structure and Spectroscopy, Vol. 1. Methodology. New York Wiley, 1999, pp 661-724. 

Guichemerre, M., Chambaud, G. and Stoll, H. (2002) Electronic structure and spectroscopy of monohalides of metals of group I-B. Chemical Physics, 280, 71-102. 

Hydroxyl radical (OH) is a key reactive intermediate in combustion and atmospheric chemistry, and it also serves as a prototypic open-shell diatomic system for investigating photodissociation involving multiple potential energy curves and nonadiabatic interactions. Previous theoretical and experimental studies have focused on electronic structures and spectroscopy of OH, especially the A2T,+-X2n band system and the predissociation of rovibrational levels of the M2S+ state,84-93 while there was no experimental work on the photodissociation dynamics to characterize the atomic products. The M2S+ state [asymptotically correlating with the excited-state products 0(1 D) + H(2S)] crosses with three repulsive states [4>J, 2E-, and 4n, correlating with the ground-state fragments 0(3Pj) + H(2S)[ in... 

Thompson MA, Zemer MC (1991) A theoretical examination of the electronic structure and spectroscopy of the photosynthetic reaction center from Rhodopseudomonas viridis. J Am Chem Soc 113 8210-8215... 

Giitlich P, Spiering, H, Hauser A (1999) Spin transition in iron(II) compounds. In Solomon El, Lever ABP (eds) Inorganic electronic structure and spectroscopy, vol. II. Wiley, New York, p 575... 

Michl, J. West, R. Electronic Structure and Spectroscopy of Polysilanes. In Silicon-based Polymers The Science and Technology of their Synthesis and Application-, Jones, R. G., Ando, W., Chojnowski, J., Eds. Kluwer Dordrecht, 2000 pp 499-529. 

A. B. P. Lever, E. S. Dodsworth, Inorganic Electronic Structure and Spectroscopy, John Wdey Sons, New York, 1999, p. 227. 

Lever ABP, Solomon El (eds) (1999) Methodology. In Inorganic Electronic Structure and Spectroscopy, vol 1. Wiley, New York, p 83... 

Kirk, Martin L., The Electronic Structure and Spectroscopy of Metallo-... 

Solomon, E. I. Lever, A. B. P. Inorganic Electronic Structure and Spectroscopy Applications and Case Studies, Wiley New York Vol. 2, 1999. 

Lever ABP, Dodsworth ES. Electrochemistry, Charge Transfer Spectroscopy and Electronic Structure. In Solomon El, Lever ABP, eds. Inorganic Electronic Structure and Spectroscopy. New York John Wiley Sons, Inc., 1999 227-291. 

Finally, a third dithiolene ligand model has been utilized with success in order to understand the electronic structure and spectroscopy of a number of oxo-molybdenum mono- and bis(dithiolenes) (23). This dithiolene ligand bonding description utilizes the symmetric and antisymmetric out-of-plane Sop p 7t orbitals, in addition to the corresponding in-plane symmetric and antisymmetric S p p orbitals. Ab initio and density functional theory (DFT) calculations have been performed on the simple dithiolene dianion, [S2C2H2]2 (23), in order to illustrate the details of this four orbital model and electron density contours of the four MOs are presented in Fig. 4. These calculations result in an isolated set of four filled dithiolene orbitals, and these are the ligand... 

The electronic structure and spectroscopy of metallo-bis(dithiolenes) are considerably more complicated than that of the metallo-mono(dithiolenes) discussed in Section II.C because there are now two dithiolene donors, which result in twice as many sulfur-based MOs that contribute to the overall metal-ligand bonding scheme. The result is an increase in the density of states in the valence region, with a concomitant increase in the number of Sdithioiene — M CT excitations. Nevertheless, numerous spectroscopic studies and bonding calculations have been undertaken in order to explain the unique electronic properties of these molecules. The fact that two dithiolene ligands are now coordinated to... 

Herein, we will discuss in detail the bonding descriptions of two common types of metallo-bis(dithiolenes) four-coordinate square-planar complexes with Ni, Pt, or Pd as the central metal ion, and five-coordinate square-pyramidal Mo and W complexes that possess a strong 7t-donor axial oxo ligand. These are arguably the most intensely studied and best understood of the metallo-bis(dithiolenes). A detailed understanding of their electronic structure and spectroscopy will certainly provide much needed insight into the bonding descriptions of new and more complex metallo-bis(dithiolene) complexes. 

Most of the late transition metals (such as Fe, Co, Rh, Ir, Ni, Pd, Pt, Cu, Au, and Zn) have been found to form bis(dithiolene) complexes. A significant amount of work has been reported on the electronic structures and spectroscopy (32), redox properties (2), as well as the conductivity (33) of bis(dithiolene) complexes. Far less has been reported on their chemical reactivity. 

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