The photochemistry of a series of alkene–O2 complexes was studied in a supersonic expansion using a resonance enhanced multiphoton ionization probe of the O(P j) photoproduct at 226 nm. The relative yield of oxygen atoms from each complex was correlated to the ionization potential of the alkene species and indicates that initial excitation of an intermolecular charge-transfer state mediates the...

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-Mx (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furf...

ELECTRON TRANSFER REACTIONS I THE REACTION CENTER ............................................. 275 Summary of Reactions To Be Considered ................................................................. 275 Electric Field Effects on Electron Transfer Reactions ............................................... 278 Electric Field Effects on the Initial Charge Separation ..............................

Amidine-appended ferrocene derivatives form a supramolecular assembly with Ru(ii)(bpy-COOH) (L)22+ complexes (bpy-COOH is 4-CO2H-4'-CH3-bpy and L = bpy, 2,2'-bipyridine or btfmbpy, 4,4'-bis (trifluoromethyl)-2,2'-bipyridine). Steady-state, time-resolved spectroscopy and kinetic isotope effects establish that the metal-to-ligand charge transfer excited states of the Ru(ii) complexes are quenched...

Determining covalent and charge-transfer contributions to bonding in solution has remained an experimental challenge. Here, the quenching of fluorescence decay channels as expressed in dips in the L-edge X-ray spectra of solvated 3d transition-metal ions and complexes was reported as a probe. With a full set of experimental and theoretical ab initio L-edge X-ray spectra of aqueous Cr(3+), inclu...

Cyanide-bridged mixed-valence complexes featuring metal(111) pentaammine acceptor sites and metal(I1) hexacyano donor sites have been investigated extensively by Vogler et aI.,l Haim and Burewicz,2 Shepherd et al.,3 and otherse4 These complexes are interesting examples of strongly covalently linked redox systems which, nevertheless, exist in valence-localized form. As mixed-valence species, the...

We show that whenever an electron transfers between closed-shell molecular fragments, the exact correlation potential of time-dependent density functional theory develops a step and peak structure in the bonding region. This structure has a density dependence that is nonlocal both in space and in time that even the exact adiabatic ground-state exchange-correlation functional fails to capture it...

the purpose of this investigation was directed to propose sensitive, accurate and reproducible methods of analysis that can be applied to determine distigmine bromide (dtb), cyclopentolate hydrochloride (cphc), diaveridine hydrochloride (dvhc) and tetrahydrozoline hydrochloride (thhc) drugs in pure form and pharmaceutical preparations via charge-transfer complex formation with 7,7,8,8-tetracyan...

Electronic structure calculations unveil structure-property relationships in doped polymers: dopants inserted the alkyl chains are stronger electron acceptors than those conjugated backbones, leading to integer charge transfer complexes.

The solid-state structures of organic charge transfer (CT) salts are critical in determining their mode of charge transport, and hence their unusual electrical properties, which range from semiconducting through metallic to superconducting. In contrast, using both theory and experiment, we show here that the conductance of metal |single molecule| metal junctions involving aromatic donor moietie...