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Free energy gap laws for the pulse-induced and stationary fluorescence quenching by reversible charge transfer in polar solutions
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10.1063/1.3528041
/content/aip/journal/jcp/134/3/10.1063/1.3528041
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/3/10.1063/1.3528041
View: Figures

Figures

Image of FIG. 1.
FIG. 1.

The Rehm–Weller plot of the Stern–Volmer constant against the free energy of ionization (Refs. 1 and 2).

Image of FIG. 2.
FIG. 2.

The multiple Rehm–Weller effect presented by a few descending branches related to different substances: amines, aromatics, and olephins (from Ref. 8).

Image of FIG. 3.
FIG. 3.

The energy scheme of the reversible photoionization, followed by spin conversion in the RIP (resulting in triplet formation) and RIP recombination and separation.

Image of FIG. 4.
FIG. 4.

The FEG laws for the Stern–Volmer constants of the pulse-induced fluorescence quenching (from left to right): in the absence of spin conversion (, red curve) or ultrafast spin conversion either without triplet formation (, blue curve) or accompanied by irreversible triplet production (, black line). The FEG law for is shown by the black dashed line. Here σ = 7.5Å, D = 100Å2/ns, ns, Å3/ns, , , λ = 0.5eV, eV, eV, T = 0.025 eV.

Image of FIG. 5.
FIG. 5.

The FEG laws for the Stern–Volmer constants of stationary fluorescence quenched by singlet RIPs recombination for three different values of its rate constant preexponent : (a), (b), and (c). The FEG law for shown by the black dashed line is much broader and its descending branch is not actually exponential. The other parameters are the same as in Fig. 4, except , λ = 0.7eV, and eV.

Image of FIG. 6.
FIG. 6.

The Λ dependence of the stationary rate constant , Eq. (2.25), at eV (blue lines). Dashed line indicates its upper limit, Eq. (2.27), while the solid straight line points out the maximal value of attained at . The black star at the bottom indicates the rate constant of a single channel (singlet) quenching, . The vertical red line separates the left region of the quasistable triplets from the right one, where the triplets are strongly quenched. Here c = 0.1M, , , , eV, eV, , and λ = 0.3eV. The other parameters are the same as in Fig. 4.

Image of FIG. 7.
FIG. 7.

The FEG laws for the Stern–Volmer constants of Eq. (2.32) at different rates of spin conversion (from right to left): (black line), (red line), (blue line), (green line), and (magenta line) at . The other parameters are the same as in Fig. 4.

Image of FIG. 8.
FIG. 8.

The FEG law for composed from the left part related to singlet production rate and the right part presented the triplet one. The rest of the parameters are the same as in Fig. 6.

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/content/aip/journal/jcp/134/3/10.1063/1.3528041
2011-01-19
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Free energy gap laws for the pulse-induced and stationary fluorescence quenching by reversible charge transfer in polar solutions
http://aip.metastore.ingenta.com/content/aip/journal/jcp/134/3/10.1063/1.3528041
10.1063/1.3528041
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