Charge transfer intermediate states

Initial Charge Transfer Intermediate State with... 

Fig. 6 Schematic illustration of the phonon-assisted exciton dissociation process. Due to the electronic state couplings, the photogenerated exciton (XT) wavepacket undergoes transitions to an interfacial charge transfer (CT) state, along with indirect XT — IS — CT transitions via an intermediate (IS) state (see panel (b)). In Ref. [52], the diabatic Hamiltonian of Eqs. (19)-(20) was parametrized for two relevant interface configurations (eclipsed (E) vs. staggered (S) as shown in panel (a)) which correspond to the configurations of Fig. 3.

D. M. Cyr, G. A. Bishea, M. G. Scranton, M. A. Johnson, J. Chem. Phys. 97, 5911 (1992). Observation of Charge-Transfer Excited States in the I CH3I, I CH3Br, and I -CH2Br2 SN2 Reaction Intermediates Using Photofragmentation and Photoelectron Spectroscopies. 

Duncan, D. C. Netzel, T. L. Hill, C. L. Early-time dynamics and reactivity of polyoxometalate excited states - identification of a short-lived lmct excited-state and a reactive long-lived charge-transfer intermediate following picosecond flash excitation of W10O32 (4-) in acetonitrile. Inorg. Chem. 1995, 34, 4640-4646. 

It is easy to see that the lowest energy 5d-excited states are exhibited by Ce3+ and Tb3+. The lowest energy charge-transfer excited states (which are also a function of the host crystal) are Eu3+ and Yb3+. All the others are intermediate in energy to those extremes of the two curves. In addition, we find that charge- transfer states occur for those trivalent ions which... 

The u.v. spectra of thiolan and thian were satisfactorily accounted for by SCF (CNDO/2) theory only if rf-orbitals were included on the sulphur atoms. The photolysis of thiolan vapour gave mainly ethylene, together with numerous other hydrocarbons, hydrogen, thiols, and thiiran, all in minor amounts. No sulphur atoms were formed, and the results were interpreted in terms of the intermediacy of two excited states, and the initial homolysis of a C—S bond, a conclusion supported by other spectroscopic data. The photochemical rearrangement of 9-thiabicyclo-[3,3,l]non-6-ene (30) proceeded via a charge-transfer intermediate (31), since photolysis in deuteriomethanol gave mainly (32) together with a little... 

A similar mean diameter i.e., 170 nm) was found for Ceo-aniline clusters in toluene - acetonitrile (1 3 v/v). This cluster formation exerted an improving impact on the performance of Ceo-based donor-acceptor dyads. For example, in aggregates of a Ceo-aniline dyad the radical pairs have a lifetime of 60 ps, while no detectable charge-transfer intermediates were noted for the isolated dyad. The close and condensed network in the cluster composites fecilitates the hopping of electrons from the parent fullerene to an adjacent one etc., progressively increasing the spatial separation between radical ions of the charge-separated state. 

Observation of Charge-transfer Excited States in the 1 CH31,1 CH3Br, and 1 CH2Br2 Sn2 Reaction Intermediates Using Photofragmentation and Photoelectron Spectroscopies. 

Duncan, D., Netzel, T. and Hdl, C. (1995). Early-Time Dynamics and Reactivity of Polyoxomet-alate Excited States. Identification of a Short-Lived LMCT Excited State and a Reactive Long-Lived Charge-Transfer Intermediate following Picosecond Flash Excitation of [Wio032] in Acetonitrile, Inorg. Chem., 34, pp. 4640-4646. 

Photochemistry.—The most recent reinvestigation of photochemical decomposition of [Co(NH3)sC1] +, using techniques of flash photolysis, chemical scavenging, and product analysis, leads to the conclusion that the reactive intermediate is probably a metastable charge-transfer excited state rather... 

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