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Transfer Transition (transfer + transition)
Selected AbstractsTheoretical investigation of electron transfer transition in tetracyanoethylene-contained organic complexesJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 9 2002Xiang-Yuan Li Abstract In this work, the authors use complete active space self-consistent field method to investigate the photoinduced charge-separated states and the electron transfer transition in complexes ethylene-tetracyanoethylene and tetramethylethylene-tetracyanoethylene. Geometries of isolated tetracyanoethylene, ethylene, and tetramethylethylene have been optimized. The ground state and the low-lying excited states of ethylene and tetracyanoethylene have been optimized. The state energies in the gas phase have been obtained and compared with the experimentally observed values. The torsion barrier of tetracyanoethylene has been investigated through the state energy calculation at different conformations. Attention has been particularly paid to the charge-separated states and the electron transfer transition of complexes. The stacked conformations of the donor,acceptor complexes have been chosen for the optimization of the ground and low-lying excited states. Equilibrium solvation has been considered by means of conductor-like screening model both in water and in dichloromethane. It has been found that the donor and tetracyanoethylene remain neutral in complexes in ground state 1A1 and in lowest triplet state 3B1, but charge separation appears in excited singlet state 1B1. Through the correction of nonequilibrium solvation energy based on the spherical cavity approximation, ,,,* electron transfer transition energies have been obtained. Compared with the experimental measurements in dichloromethane, the theoretical results in the same solvent are found higher by about 0.5 eV. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 874,886, 2002 [source] Photoreduction of iron protoporphyrin IX chloride in non-ionic triton X-100 micelle studied by electronic absorption and resonance Raman spectroscopyJOURNAL OF RAMAN SPECTROSCOPY, Issue 3 2001P. K. Shantha Resonance Raman and electronic absorption studies of iron protoporphyrin IX chloride (hemin) in non-ionic Triton X-100 micelle in the absence and presence of hindered imidazole (2-methylimidazole and 1,2-dimethylimidazole) and unhindered imidazole under various experimental conditions are reported. Hemin undergoes photoreduction at the metal center, both in the absence and presence of hindered imidazole, in anaerobic, alkaline and neutral pH conditions on photoexcitation by laser radiation at 441.6 and 457.9 nm. It is inferred from this study that only the monomer hemin encapsulated within the micelle under the alkaline pH conditions is photoreducible. The photoreduction of hemin in this micelle occurs from an electron transfer as a result of dissociation of coordinated hydroxyl ion to the iron atom in the photoexcited state, which may also involve the OH,Fe charge transfer transition around 360 nm. Copyright © 2001 John Wiley & Sons, Ltd. [source] Metal,thiolate bonds in bioinorganic chemistryJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 12 2006Edward I. Solomon Abstract Metal,thiolate active sites play major roles in bioinorganic chemistry. The MSthiolate bonds can be very covalent, and involve different orbital interactions. Spectroscopic features of these active sites (intense, low-energy charge transfer transitions) reflect the high covalency of the MSthiolate bonds. The energy of the metal,thiolate bond is fairly insensitive to its ionic/covalent and ,/, nature as increasing MS covalency reduces the charge distribution, hence the ionic term, and these contributions can compensate. Thus, trends observed in stability constants (i.e., the Irving,Williams series) mostly reflect the dominantly ionic contribution to bonding of the innocent ligand being replaced by the thiolate. Due to high effective nuclear charges of the CuII and FeIII ions, the cupric, and ferric,thiolate bonds are very covalent, with the former having strong , and the latter having more , character. For the blue copper site, the high , covalency couples the metal ion into the protein for rapid directional long range electron transfer. For rubredoxins, because the redox active molecular orbital is , in nature, electron transfer tends to be more localized in the vicinity of the active site. Although the energy of hydrogen bonding of the protein environment to the thiolate ligands tends to be fairly small, H-bonding can significantly affect the covalency of the metal,thiolate bond and contribute to redox tuning by the protein environment. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1415,1428, 2006 [source] A new molecular mechanics force field for the oxidized form of blue copper proteinsJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2002Peter Comba Abstract A molecular mechanics force field for blue copper proteins has been developed, based on a rigid potential energy surface scan of the CuII/His/His/Cys/Met chromophore, using DFT (B3LYP) calculations and the AMBER force field for the protein backbone. The strain,energy-minimized structures of the model chromophore alone are in excellent agreement with the DFT-optimized structure, and those of the entire set of cupredoxins (five structures are considered) are, within the experimental error limits, in good agreement with the single crystal structural data. However, the structural variation in the computed structures is much smaller than those in the experimental structures. It is shown that, due to the large error limits in the experimental data, a validation of the force field with experimental structural data is impossible because, within the error limits, all experimental structures considered are virtually identical. A validation on the basis of spectroscopic data and their correlation with experimental and computed structural data is proposed, and, as a first example, the correlation of intensity ratios of the charge transfer transitions with a specific distortion mode is presented. The quality of the correlation, using the computed structures, is higher than that with the X-ray structures, and this indicates that the computed structures are meaningful. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 697,705, 2002 [source] Pressure dependence of the optical properties of wurtzite and rock-salt Zn1,xCoxO thin filmsPHYSICA STATUS SOLIDI (B) BASIC SOLID STATE PHYSICS, Issue 1 2007J. A. Sans Abstract In this paper we investigate the electronic structure of Zn1,xCoxO by means of optical absorption measurements under pressure. Thin films of Zn1,xCoxO with different Co content (from 1 to 30%) were prepared by pulsed laser deposition on mica substrates. Absorption spectra exhibit three main features that are clearly correlated to the Co content in the films: (i) absorption peaks in the infrared associated to crystal-field-split internal transitions in the Co 3d shell, with very small pressure coefficients due to their atomic character; (ii) a broad absorption band below the fundamental edge associated to charge transfer transitions, that exhibit relatively large pressure coefficients, indicating that the Co 3d final states must be strongly hybridized to the conduction band; and (iii) a blue-shifted fundamental absorption edge associated to band to band transitions with a pressure coefficient close to that of pure ZnO. In the up-stroke the transition pressure from wurtzite to rock-salt phase decrease almost linearly as the Co increases, from 9.5 GPa in pure ZnO to about 6.5 GPa for x = 30%. In the down-stroke pressure we observe a similar behavior, yielding a metastable rock-salt phase at room pressure, after a pressure cycle up to 15 GPa. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] | ||||||||||