Energy transfer long range

Fig. 1.25 Orbital comparison of long- and short-range quenching of an excited state (D ) and a ground state acceptor (A) by a Forster energy transfer (long-range), b Dexter energy transfer (short-range) and c photoinduced electron transfer (short range)...

Blumberger J, Klein ML (2006) Reorganization free energies for long-range eleetron transfer in a porphyrin-binding four-helix bundle protein. J Am Chem Soc 128 13854... 

With this convention, we can now classify energy transfer processes either as resonant, if IA defined in equation (A3.13.81 is small, or non-resonant, if it is large. Quite generally the rate of resonant processes can approach or even exceed the Leimard-Jones collision frequency (the latter is possible if other long-range potentials are actually applicable, such as by pennanent dipole-dipole interaction). 

Resonant rotational to rotational (R-R) energy transfer may have rates exceeding the Leimard-Jones collision frequency because of long-range dipole-dipole interactions in some cases. Quasiresonant vibration to rotation transfer (V-R) has recently been discussed in the framework of a simple model [57]. 

Sharma R D and Brau C A 1969 Energy transfer in near-resonant molecular collisions due to long-range forces with application to transfer of vibrational energy from the mode of CO2 to N2 J. Chem. Phys. 50 924-30... 

More recently Andrews and Juzeliunas [6, 7] developed a unified tlieory that embraces botli radiationless (Forster) and long-range radiative energy transfer. In otlier words tliis tlieory is valid over tire whole span of distances ranging from tliose which characterize molecular stmcture (nanometres) up to cosmic distances. It also addresses tire intennediate range where neitlier tire radiative nor tire Forster mechanism is fully valid. Below is tlieir expression for tire rate of pairwise energy transfer w from donor to acceptor, applicable to transfer in systems where tire donor and acceptor are embedded in a transparent medium of refractive index ... 

Whereas the spot positions carry information about the size of the surface unit cell, the shapes and widths of the spots, i.e. the spot profiles, are influenced by the long range arrangement and order of the unit cells at the surface. If vertical displacements (steps, facets) of the surface unit cells are involved, the spot profiles change as a function of electron energy. If all surface unit cells are in the same plane (within the transfer width of the LEED optics), the spot profile is constant with energy. 

As an example of a multilayer system we reproduce, in Fig. 3, experimental TPD spectra of Cs/Ru(0001) [34,35] and theoretical spectra [36] calculated from Eq. (4) with 6, T) calculated by the transfer matrix method with M = 6 on a hexagonal lattice. In the lattice gas Hamiltonian we have short-ranged repulsions in the first layer to reproduce the (V X a/3) and p 2 x 2) structures in addition to a long-ranged mean field repulsion. Second and third layers have attractive interactions to account for condensation in layer-by-layer growth. The calculations not only successfully account for the gross features of the TPD spectra but also explain a subtle feature of delayed desorption between third and second layers. As well, the lattice gas parameters obtained by this fit reproduce the bulk sublimation energy of cesium in the third layer. 

The small effect that has been observed can be quantitatively accounted for via Forster-type long-range singlet energy transfer,(1,46,48)... 

All of the examples of singlet energy transfer we have considered take place via the long-range resonance mechanism. When the oscillator strength of the acceptor is very small (for example, n-> n transitions) so that the Fdrster critical distance R0 approaches or is less than the collision diameter of the donor-acceptor pair, then all evidence indicates that the transfer takes place at a diffusion-controlled rate. Consequently, the transfer mechanism should involve exchange as well as Coulomb interaction. Good examples of this type of transfer have been provided by Dubois and co-workers.(47-49)... 

Scholes, G. D. 2003. Long-range resonance energy transfer in molecular systems. Annu. Rev. Phys. Chem. 54 57-87. 

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