On the Physical Nature of Uranyl Charge Transfer Vibronic Interactions

2003 ◽  
Vol 802 ◽  
Author(s):  
X. Y. Chen ◽  
L. F. Rao ◽  
G. K. Liu
Keyword(s):  
Charge Transfer ◽  
Physical Nature ◽  
Spectroscopic Properties ◽  
Uranyl Ions ◽  
Phonon Interaction ◽  
Theoretical Understanding ◽  
Vibronic Interactions ◽  
Photochemical Properties ◽  
Predictive Understanding ◽  
Theory And Experiment

ABSTRACTWe address the electronic properties of uranyl ions in solids and solutions with an emphasis in theoretical understanding of charge transfer vibronic transitions and luminescence dynamics the O-U-O species. A general theory of ion-phonon interaction has been modified for modeling and simulating multi-phonon vibronic spectra. Spectroscopic data for uranyl ions in crystals and solutions have been analyzed to achieve a predictive understanding of the uranyl-ligand vibronic interactions. By adjusting the Huang-Rhys ion-phonon interaction parameters, an excellent agreement between theory and experiment has been accomplished for uranyl ions in the ligand environments we studied. Our modeling and simulation provide insights into the physical nature of uranyl vibronic interaction and its influence on spectroscopic properties, which are commonly utilized in characterizing photochemical properties of uranyl in complexes.

Synthesis and Photochemical Properties of Re(I) Tricarbonyl Complexes Bound to Thione and Thiazole-2-ylidene Ligands

2020 ◽  
Author(s):  
Matthew Stout ◽  
Brian Skelton ◽  
Alexandre N. Sobolev ◽  
Paolo Raiteri ◽  
Massimiliano Massi ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Excited States ◽  
Ligand Exchange ◽  
Ligand Substitution ◽  
Bidentate Ligand ◽  
The Other ◽  
Ligand Exchange Reaction ◽  
Multiple Products ◽  
Ligand Charge Transfer ◽  
Photochemical Properties

<p>Three Re(I) tricarbonyl complexes, with general formulation Re(N^L)(CO)<sub>3</sub>X (where N^L is a bidentate ligand containing a pyridine functionalized in the position 2 with a thione or a thiazol-2-ylidene group and X is either chloro or bromo) were synthesized and their reactivity explored in terms of solvent-dependent ligand substitution, both in the ground and excited states. When dissolved in acetonitrile, the complexes bound to the thione ligand underwent ligand exchange with the solvent resulting in the formation of Re(NCMe)<sub>2</sub>(CO)<sub>3</sub>X. The exchange was found to be reversible, and the starting complex was reformed upon removal of the solvent. On the other hand, the complexes appeared inert in dichloromethane or acetone. Conversely, the complex bound to the thiazole-2-ylidene ligand did not display any ligand exchange reaction in the dark, but underwent photoactivated ligand substitution when excited to its lowest metal-to-ligand charge transfer manifold. Photolysis of this complex in acetonitrile generated multiple products, including Re(I) tricarbonyl and dicarbonyl solvato-complexes as well as free thiazole-2-ylidene ligand.</p>

Optical Spectroscopic Studies of a Soluble Fluorene-Based Conjugated Polymer: A Hydrostatic Pressure and Temperature Study

2001 ◽  
Vol 708 ◽  
Author(s):  
S. Guha ◽  
J.D. Rice ◽  
C. M. Martin ◽  
W. Graupner ◽  
M. Chandrasekhar ◽  
...  
Keyword(s):  
Hydrostatic Pressure ◽  
Conjugated Polymer ◽  
Spectroscopic Properties ◽  
Spectroscopic Studies ◽  
Phonon Interaction ◽  
Optical Studies ◽  
Strong Electron ◽  
Conjugated Molecules ◽  
Electron Phonon Interaction ◽  
Backbone Conformation

ABSTRACTSpectroscopic properties of conjugated molecules/polymers have varying degrees of sensitivity to backbone conformation. Optical studies are presented as a function of temperature and hydrostatic pressure, using photoluminescence and Raman scattering from two polymers with distinct differences in their backbone conformation, namely, polyfluorene (PF) and ladder type poly(para-phenylene)(m-LPPP). In contrast to the photoluminescence (PL) vibronics in mLPPP, the 0-0 PL vibronic peak in PF shows a red-shift with increasing temperatures. Pressure studies reveal that the PL spectrum of PF red-shifts and broadens with increasing pressures. The phonon lines in PF show an antiresonance effect at higher pressures indicating a strong electron-phonon interaction.

scholarly journals Combining Theory and Experiment for Understanding of Ultrafast Photoinduced Charge-Transfer Processes

2020 ◽  
pp. 91-99
Author(s):  
Eric Vauthey
Keyword(s):  
Charge Transfer ◽  
Condensed Phase ◽  
Photoinduced Charge Transfer ◽  
Transfer Processes ◽  
Experimental Spectroscopy ◽  
Photoinduced Charge ◽  
Theory And Experiment

This article gives a brief overview of the longstanding collaboration between our experimental spectroscopy group in Geneva and the theoretical group lead by Prof. A.I. Ivanov in Volgograd. This fruitful collaboration resulted in a significant increase of our understanding of the dynamics of several ultrafast chargetransfer processes in the condensed phase.

Alkyl pyridinium iodocyanocuprate(i) chains (RPy)2[Cu2I3(CN)]: insight into structural, electronic and spectroscopic properties

2020 ◽  
Vol 49 (5) ◽  
pp. 1492-1500
Author(s):  
Taylor C. Wells ◽  
Michaela E. Streep ◽  
Abigail L. Martucci ◽  
Aaron D. Nicholas ◽  
Robert D. Pike
Keyword(s):  
Hydrogen Bonding ◽  
Charge Transfer ◽  
Spectroscopic Properties ◽  
Insight Into

Reaction of RPyI, CuI, and CuCN produces anionic iodocyanocuprate(i) chains, (RPy)2[Cu2I3CN] which exhibit charge transfer that is influenced by the hydrogen bonding between the cation and the triiodide groups.

Structural characterization, optical properties and photocatalytic activity of MOF-5 and its hydrolysis products: implications on their excitation mechanism

RSC Advances ◽  
2015 ◽  
Vol 5 (89) ◽  
pp. 73112-73118 ◽  
Author(s):  
N. A. Rodríguez ◽  
R. Parra ◽  
M. A. Grela
Keyword(s):  
Optical Properties ◽  
Photocatalytic Activity ◽  
Charge Transfer ◽  
Structural Characterization ◽  
Excitation Mechanism ◽  
Hydrolysis Products ◽  
Ligand Charge Transfer ◽  
Photochemical Properties ◽  
Hydrolysis Of

Hydrolysis of MOF-5 gives place to a mixture of two compounds: MOF-5W and zinc terephthalate dihydrate. The analysis of optical and photochemical properties allows to infer the preeminence of a ligand to ligand charge-transfer.

scholarly journals Substitution Effect on the Charge Transfer Processes in Organo-Imido Lindqvist-Polyoxomolybdate

Molecules ◽  
2018 ◽  
Vol 24 (1) ◽  
pp. 44 ◽  
Author(s):  
Patricio Hermosilla-Ibáñez ◽  
Kerry Wrighton-Araneda ◽  
Walter Cañón-Mancisidor ◽  
Marlen Gutiérrez-Cutiño ◽  
Verónica Paredes-García ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Theoretical Study ◽  
Bathochromic Shift ◽  
Substitution Effect ◽  
Spectroscopic Properties ◽  
Electrochemical Studies ◽  
Redox Potentials ◽  
Metal Centre ◽  
Transfer Processes ◽  
Organic Fragment

Two new aromatic organo-imido polyoxometalates with an electron donor triazole group ([n-Bu4N]2[Mo6O18NC6H4N3C2H2]) (1) and a highly conjugated fluorene ([n-Bu4N]2[Mo6O18NC13H9]) (2) have been obtained. The electrochemical and spectroscopic properties of several organo-imido systems were studied. These properties were analysed by the theoretical study of the redox potentials and by means of the excitation analysis, in order to understand the effect on the substitution of the organo-imido fragment and the effect of the interaction to a metal centre. Our results show a bathochromic shift related to the charge transfer processes induced by the increase of the conjugated character of the organic fragment. The cathodic shift obtained from the electrochemical studies reflects that the electronic communication and conjugation between the organic and inorganic fragments is the main reason of this phenomenon.

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