On the Interaction of Radiation with Matter and on Fluorescent Exciting Power

Kennard, E. H.

doi:10.1103/physrev.28.672

Cited by 53 publications

(26 citation statements)

References 2 publications

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“…(8) • t ,.8-Non-radiative band-to-band transitions are frequently a significant source of E-to-G relaxation. l\'e assume that the rate of induced G-to-E transitions given by (6) is large with respect to all spontaneous excitations.…”

Section: Ti-ieorymentioning

confidence: 99%

Some Thermodynamics of Photochemical Systems

Ross¹

1967

The Journal of Chemical Physics

339

251

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A limit on the thermodynamic potential difference between the ground and excited states of any photochemical system is established by evaluating the potential difference at which the rate of photon absorption and emission are equal; the relationship between absorption and emission is given by a Planck-law relation, provided that there is thermal equilibrium between the sublevels of each electronic band. The actual potential developed may be evaluated if the quantum yield of luminescence is known. The maximum amount of power storage obtainable is evaluated by lowering the potential difference until the product of the potential difference and the fraction of the quanta retained is maximized. The history and applications of the Planck-law relation between absorption and emission spectra are discussed briefly, and applications of the potential difference calculation are mentioned.

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Section: Ti-ieorymentioning

confidence: 99%

Some Thermodynamics of Photochemical Systems

Ross¹

1967

The Journal of Chemical Physics

339

251

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“…In 1918 Kennard [2] found a simple relationship between fluorescence and absorption spectra and later revised the derivation on the basis of the emerging quantum theory [3]. The relationship, which will be found below as Eq.…”

Section: Meaning Of Equilibration In An Excited Statementioning

confidence: 99%

Excited-State Equilibration and the Fluorescence-Absorption Ratio

Knox

1999

Acta Phys. Pol. A

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In any complex system at temperature T the absorption cross-section and fluorescent power at a given photon energy are connected by a simple relation if the system is in thermal equilibrium while occupying one particular electronic excited state. Although this situation is impossible in principle because of finite excited-state lifetimes, it is often approximated to the extent that the simple relation, which is expressed as a linear function of energy with slope -1/kBT, holds in a variety of cases. (The usual symbols for Boltzmann's constant and absolute temperature are used.) Observed deviations are of two principal kinds: a slope characteristic of some temperature T* other than ambient, and departures from a single pure straight line. The latter may include seemingly random variations and in some cases multiple regions of straight-line behavior. We have recently introduced an effective temperature T* (E), derived from the actual local slope of the putative straight line at energy E, which turns out to be a very sensitive detector of deviations from the ideal and, we believe, from equilibrium in the excited state. Plots of T* (E) display a variety of features. An anomaly in the T* (E) spectrum of chlorophyll a can be analyzed on this model, indicating a second weakly fluorescent state about 70 meV below the well-known Qy band. The cases of chlorophyll and many others are included in a selective review of applications of the universal relation to fluorescent systems.

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“…23, p. 222͒ but can also be derived for Gaussian spectral lines 24 by using the Kennard-Stepanov relation. 25,26 A simple model for Eq. ͑5͒ can be found in Ref.…”

Section: The Fö Rster Rate Between Identical Molecules With Gaussmentioning

confidence: 99%

Polaron-exciton model of resonance energy transfer

Markvart

Greef²

2004

The Journal of Chemical Physics

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It is shown that Förster's expression for the electronic energy transfer rate can be recast in a form predicted for exciton motion that interacts strongly with molecular vibrations. Using a simple model based on the Kennard-Stepanov theory, Förster's expression for the spectral overlap is shown to be of a thermally activated form, as obtained previously by multiphonon theory. In contrast, the high-frequency internal vibrations contribute a factor which results from tunneling through a potential barrier between potential curves in the configuration coordinate diagram. We thus show that resonance energy transfer is equivalent to phonon-assisted hopping of a trapped excitonic polaron.

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On the Interaction of Radiation with Matter and on Fluorescent Exciting Power

Cited by 53 publications

References 2 publications

Some Thermodynamics of Photochemical Systems

Some Thermodynamics of Photochemical Systems

Excited-State Equilibration and the Fluorescence-Absorption Ratio

Polaron-exciton model of resonance energy transfer

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