Self-Interaction Corrected Density Functional Theory for the Study of Intramolecular Electron Transfer Dynamics in Radical Carbocations

2007 ◽  
Vol 111 (51) ◽  
pp. 13528-13536 ◽  
Author(s):  
Ivano Tavernelli
Keyword(s):  
Density Functional Theory ◽  
Electron Transfer ◽  
Density Functional ◽  
Intramolecular Electron Transfer ◽  
Functional Theory

Back donation, intramolecular electron transfer and N–O bond scission targeting nitrogen oxyanion reduction: how can a metal complex assist?

2021 ◽  
Vol 50 (6) ◽  
pp. 2149-2157
Author(s):  
Daniel M. Beagan ◽  
Alyssa C. Cabelof ◽  
Kenneth G. Caulton
Keyword(s):  
Density Functional Theory ◽  
Electron Transfer ◽  
Metal Complex ◽  
Density Functional ◽  
Oxidation States ◽  
Intramolecular Electron Transfer ◽  
Functional Theory ◽  
Bond Scission ◽  
Nitrogen Oxidation ◽  
Back Donation

A density functional theory exploration studies a range of ancillary coordinated ligands accompanying nitrogen oxyanions with the goal of promoting back donation towards varied nitrogen oxidation states.

scholarly journals A molecular density functional theory approach to electron transfer reactions

2019 ◽  
Vol 10 (7) ◽  
pp. 2130-2143 ◽  
Author(s):  
Guillaume Jeanmairet ◽  
Benjamin Rotenberg ◽  
Maximilien Levesque ◽  
Daniel Borgis ◽  
Mathieu Salanne
Keyword(s):  
Density Functional Theory ◽  
Electron Transfer ◽  
Density Functional ◽  
Transfer Reactions ◽  
Interfacial Water ◽  
Theory Approach ◽  
Computational Tool ◽  
Functional Theory ◽  
Electron Transfer Reactions ◽  
Molecular Density

Molecular density functional theory, an efficient computational tool, provides new insights into the study of electron transfer reactions in bulk and interfacial water.

scholarly journals Investigation of the position of the radical in z3-ions resulting from electron transfer dissociation using infrared ion spectroscopy

2019 ◽  
Vol 217 ◽  
pp. 434-452 ◽  
Author(s):  
Lisanne J. M. Kempkes ◽  
Jonathan Martens ◽  
Giel Berden ◽  
Kas J. Houthuijs ◽  
Jos Oomens
Keyword(s):  
Mass Spectrometry ◽  
Density Functional Theory ◽  
Electron Transfer ◽  
Density Functional ◽  
Electron Transfer Dissociation ◽  
Open Shell ◽  
Molecular Structures ◽  
Functional Theory ◽  
Ion Spectroscopy ◽  
Molecular Dynamics Calculations

The molecular structures of six open-shell z3-ions resulting from electron transfer dissociation mass spectrometry (ETD MS) were investigated using infrared ion spectroscopy in combination with density functional theory and molecular mechanics/molecular dynamics calculations.

scholarly journals Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling

2020 ◽  
Vol 22 (19) ◽  
pp. 10609-10623 ◽  
Author(s):  
Pavan Kumar Behara ◽  
Michel Dupuis
Keyword(s):  
Density Functional Theory ◽  
Electron Transfer ◽  
Density Functional ◽  
Transition Element ◽  
Electronic Coupling ◽  
Functional Theory ◽  
Extended Systems ◽  
Periodic Dft

CP2K implementation describing electron transfer in extended systems treated by periodic-DFT, including the calculation of electronic coupling transition element VAB.

A density functional theory and spectroscopic study of intramolecular quenching of metal-to-ligand charge-transfer excited states in some mono-bipyridine ruthenium(II) complexes

2014 ◽  
Vol 92 (10) ◽  
pp. 996-1009 ◽  
Author(s):  
Shivnath Mazumder ◽  
Ryan A. Thomas ◽  
Richard L. Lord ◽  
H. Bernhard Schlegel ◽  
John F. Endicott
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Excited States ◽  
Lower Energy ◽  
Density Functional ◽  
Dimethyl Sulfide ◽  
Intramolecular Electron Transfer ◽  
Functional Theory ◽  
Ligand Charge Transfer

The complexes [Ru(NCCH3)4bpy]2+ and [Ru([14]aneS4)bpy]2+ ([14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane, bpy = 2,2′-bipyridine) have similar absorption and emission spectra but the 77 K metal-to-ligand charge-transfer (MLCT) excited state emission lifetime of the latter is less than 0.3% that of the former. Density functional theory modeling of the lowest energy triplet excited states indicates that triplet metal centered (3MC) excited states are about 3500 cm−1 lower in energy than their 3MLCT excited states in both complexes. The differences in excited state lifetimes arise from a much larger coordination sphere distortion for [Ru(NCCH3)4bpy]2+ and the associated larger reorganizational barrier for intramolecular electron transfer. The smaller ruthenium ligand distortions of the [Ru([14]aneS4)bpy]2+ complex are apparently a consequence of stereochemical constraints imposed by the macrocyclic [14]aneS4 ligand, and the 3MC excited state calculated for the unconstrained [Ru(S(CH3)2)4bpy]2+ complex (S(CH3)2 = dimethyl sulfide) is distorted in a manner similar to that of [Ru(NCCH3)4bpy]2+. Despite the lower energy calculated for its 3MC than 3MLCT excited state, [Ru(NCCH3)4bpy]2+ emits strongly in 77 K glasses with an emission quantum yield of 0.47. The emission is biphasic with about a 1 μs lifetime for its dominant (86%) emission component. The 405 nm excitation used in these studies results in a significant amount of photodecomposition in the 77 K glasses. This is a temperature-dependent biphotonic process that most likely involves the bipyridine-radical anionic moiety of the 3MLCT excited state. A smaller than expected value found for the radiative rate constant is consistent with a lower energy 3MC than 3MLCT state.

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