Theory and applications of charge-transfer-to-solvent spectra

Blandamer, Michael J.; Fox, Malcom F.

doi:10.1021/cr60263a002

Cited by 377 publications

(313 citation statements)

References 101 publications

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“…The rigidity of the CC2 method was also evaluated by comparison with experimental data available for the nitrate anion. [55] Excellent agreement was observed.…”

Section: Methodsmentioning

confidence: 71%

Kinetic Stability and Propellant Performance of Green Energetic Materials

Rahm

Brinck

2010

Chemistry A European J

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Outside contact: Cells in multicellular organisms regulate their adhesion through specialized integrin receptors, which relay signals bidirectionally between the inside and outside of cells. The transmembrane domains (see picture, blue; the integrin–talin complex is red and green) of integrins are the center of the signaling process. Recently, structures of these domains have been reported that shed light on the signal transduction mechanism.

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“…The rigidity of the CC2 method was also evaluated by comparison with experimental data available for the nitrate anion. [55] Excellent agreement was observed.…”

Section: Methodsmentioning

confidence: 71%

Kinetic Stability and Propellant Performance of Green Energetic Materials

Rahm

Brinck

2010

Chemistry A European J

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“…2,3 Following the dissociation of this CTTS state, a geminate pair of the electron and the residual radical (such as hydroxyl for HO -and iodine atom for I -) is formed in less than 200 fs. Some of these geminate pairs recombine (typically, within 0.5-1 ns), while the rest escape to the solvent bulk, yielding "free" electrons and radicals that undergo slow recombination and other secondary reactions.…”

Section: Introductionmentioning

confidence: 99%

Electron Photodetachment from Aqueous Anions. 3. Dynamics of Geminate Pairs Derived from Photoexcitation of Mono- vs Polyatomic Anions

Lian

Oulianov²,

Crowell³

et al. 2006

J. Phys. Chem. A

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Photostimulated electron detachment from aqueous inorganic anions is the simplest example of solvent-mediated electron transfer. As such, this photoreaction became the subject of many ultrafast studies. Most of these studied focussed on the behavior of halide anions, in particular, iodide, that is readily accessible in the UV. In this study, we contrast the behavior of these halide anions with that of small polyatomic anions, such as pseudohalide anions (e.g., HS -) and common polyvalent anions (e.g., kinetics. These analyses suggest that for polyatomic anions (including all polyvalent anions studied) the initial electron distribution has a broad component, even at relatively low photoexcitation energy. There seem to be no well-defined threshold energy below which the broadening of the distribution does not occur, as is the case for halide anions.Direct ionization to the conduction band of water is the most likely photoprocess broadening the electron distribution. The constancy of (near-unity) prompt quantum yields vs. the excitation energy as the latter is scanned across the lowest charge-transferto-solvent band of the anion is observed for halide anions and Fe(CN) 6 4-but not for other anions: the prompt quantum yields are considerably less than unity and depend strongly on the excitation energy. Our study suggests that halide anions are in the class of their own; photodetachment from polyatomic, especially polyvalent, anions follows a different set of rules.

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“…Thus, there has been an increasing amount of research into the simplest class of solution-phase charge transfer reactions, charge-transfer-to-solvent ͑CTTS͒ systems. 1 CTTS transitions result from additional bound states for an ionizable electron that are introduced by solvent stabilization. Upon photoexcitation from the ground state to a higher energy solvent-supported state, delayed electron detachment is often observed.…”

Section: Introductionmentioning

confidence: 99%

“…Though the seminal work on CTTS systems began decades ago, 1 there has been a recent revival of interest in CTTS reactions arising from the ability to examine dynamics on subpicosecond time scales with ultrafast lasers. [2][3][4][5] The aqueous halides have been the subject of most of the attention, providing insight into the motions of arguably the most important solvent, water.…”

Section: Introductionmentioning

confidence: 99%

The role of electronic symmetry in charge-transfer-to-solvent reactions: Quantum nonadiabatic computer simulation of photoexcited sodium anions

Smallwood

Bosma

Larsen

et al. 2003

The Journal of Chemical Physics

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Since charge-transfer-to-solvent (CTTS) reactions represent the simplest class of solvent-driven electron transfer reactions, there has been considerable interest in understanding the solvent motions responsible for electron ejection. The major question that we explore in this paper is what role the symmetry of the electronic states plays in determining the solvent motions that account for CTTS. To this end, we have performed a series of one-electron mixed quantum/classical nonadiabatic molecular dynamics simulations of the CTTS dynamics of sodide, Na−, which has its ground-state electron in an s orbital and solvent-supported CTTS excited states of p-like symmetry. We compare our simulations to previous theoretical work on the CTTS dynamics of the aqueous halides, in which the ground state has the electron in a p orbital and the CTTS excited state has s-like symmetry. We find that the key motions for Na− relaxation involve translations of solvent molecules into the node of the p-like CTTS excited state. This solvation of the electronic node leads to migration of the excited CTTS electron, leaving one of the p-like lobes pinned to the sodium atom core and the other extended into the solvent; this nodal migration causes a breakdown of linear response. Most importantly, for the nonadiabatic transition out of the CTTS excited state and the subsequent return to equilibrium, we find dramatic differences between the relaxation dynamics of sodide and the halides that result directly from differences in electronic symmetry. Since the ground state of the ejected electron is s-like, detachment from the s-like CTTS excited state of the halides occurs directly, but detachment cannot occur from the p-like CTTS excited state of Na− without a nonadiabatic transition to remove the node. Thus, unlike the halides, CTTS electron detachment from sodide occurs only after relaxation to the ground state and is a relatively rare event. In addition, the fact that the electronic symmetry of sodide is the same as for the hydrated electron enables us to directly study the effect of a stabilizing atomic core on the properties and solvation dynamics of solvent-supported electronic states. All the results are compared to experimental work on Na− CTTS dynamics, and a unified picture for the electronic relaxation for solvent-supported excited states of any symmetry is presented.

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Theory and applications of charge-transfer-to-solvent spectra

Cited by 377 publications

References 101 publications

Kinetic Stability and Propellant Performance of Green Energetic Materials

Kinetic Stability and Propellant Performance of Green Energetic Materials

Electron Photodetachment from Aqueous Anions. 3. Dynamics of Geminate Pairs Derived from Photoexcitation of Mono- vs Polyatomic Anions

The role of electronic symmetry in charge-transfer-to-solvent reactions: Quantum nonadiabatic computer simulation of photoexcited sodium anions

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