SCHEIBE AGGREGATES

Scheibe aggregates (also called J-aggregates) are a type of LangmuirBlodgett thin lms that were independently discovered in 1936 by Gnther Scheibe (Scheibe, 1936) in Germany and E.E. Jelly (Jelly, 1936) in Englandhence their names. They comprise compact and regular arrangements of dye molecules composed of chromophores and fatty acids that can be designed to pre-selected specications. These molecular monolayers exhibit very efcient light capture followed by energy transfer to acceptor molecules present in the lm at very low acceptor-todonor ratios (as low as 1:10,000), giving the efciency of energy transfer to acceptors as high as 50% (Moebius, 1989). In the late 1960s and in the 1970s, Kuhn, Moebius and co-workers (Czikkely et al., 1969) studied the effects of irradiation with ultraviolet or visible light and measured the strongly quenched donor uorescence in these aggregates. An acceptor uorescence line appeared whose amplitude was almost equal to that of the primary donor spectral line but its peak was slightly redshifted, which was interpreted as evidence that the aggregate acts as a cooperative molecular array. After absorbing a photon, the energy moves in the form of an exciton travelling laterally over distances of up to 100 nm to a particular acceptor dye in the vicinity. The efciency of this energy transfer mechanism is strongly linked with the rigidity of the aggregate and its regular order. Surprisingly, the capture of energy by an acceptor molecule improves with the ambient temperature. Optimal efciency is achieved at fairly low acceptor-to-donor ratios as mentioned above. Numerous technological applications of these molecular systems have been developed, including photographic and photo-detection processes as well as solar energy cell components (Inoue, 1985). Several theoretical models of Scheibe aggregates have been developed over the years. The Frenkel exciton picture with the inclusion of diagonal disorder in molecular chains with nearest-neighbor interactions was adopted to describe the pseudo-isocyanine aggregate (Knapp, 1984) and was later extended to account for off-diagonal disorder. Subsequently, linear models of exciton propagation in the presence of shallow impurity potentials at acceptor sites showed (Bartnik et al., 1992) close quantitative agreement with experiment. These impurity potentials were usually assumed to be of a square-well type and their depth as well as spatial extent were parameters subject to optimization schemes. Interestingly, shallow impurity levels gave better capture properties than deep ones. There have also been a number of theoretical studies advocating a role played by nonlinearity in the propagation of excitonic modes in Scheibe aggregates.

AQ:1
OK

traveling

The main reason for this claim is due to exciton phonon coupling whose strength for mero-cyanine was experimentally determined as approximately = 29 meV (Inoue, 1985) and theoretically estimated as = 26 meV (Spano et al., 1990). In general three types of excitonic models can be applied: (a) a nearly free delocalized case, (b) a small polaron limit, and (c) the nonlinear self-trapped exciton state. The applicability criterion for these models involves a phase diagram in terms of two characteristic parameters: g = 2 /J and = h/2 J , where h is Plancks constant, is the phonon frequency, and J is the exciton hopping constant. With the phonon energy approximately 30 meV, J in the range between 50 and 150 meV, and the excitonphonon coupling constant ranging from 25 to 100 meV, the outcome of this parameter determination is yet inconclusive (Tuszy ski n et al., 1999). It is important to stress that these systems should be modeled as two-dimensional structures. Continuous two-dimensional models with nonlinear terms have been developed that treat phonons classically and effectively eliminate them via an adiabatic approximation (Huth et al., 1989), leading to a 2-d radially symmetric cubic nonlinear Schrdinger equation, where the energy transfer takes place through soliton-like ring waves with a characteristic collapse time signifying the exciton lifetime. More recent models involving nonlinear equations of the cubic Schrdinger type also account for the presence of Gaussian impurity potentials (Christiansen et al., 1998). Finally, it is necessary to include radiative losses in modeling the propagation of an exciton domain. Formally, this can be accomplished by adding an imaginary term to the exciton-phonon part of the Hamiltonian that describes the corresponding loss of energy of excitons as they collide with phonons in the thin-lm lattice. Consequently, it has been shown that the rate of excitonic energy loss by a coherent exciton domain covering an area comprised of N molecules is proportional to its size, N , and can be expressed as: krad = N nanoseconds 1 . It has also been demonstrated that the characteristic time for radiative losses is approximately proportional to the absolute temperature T divided by 3000 K and the result is expressed in nanoseconds (Moebius & Kuhn, 1988). In other words, the radiative decay time in nanoseconds is given by rad = (T /3000) K. For example, at room temperature, a coherent exciton domain comprised of 100 lattice sites has a decay time of 0.1 ns = 100 ps compared to a ight time of only 2 ps, which means that radiative losses will not destroy the coherence of the exciton domain unless it is very large (approximately 10,000 lattice sites). A comprehensive review of the key processes taking place in exciton energy transfer

hyphen

hyphen

$T$

SCHEIBE AGGREGATES in Scheibe aggregates (time of ight, radiative losses, excitonphonon interaction, and diffusion on the 2-d lattice) can be found in Tuszy ski et al. (1999). n JACK A. TUSZYNSKI See also Excitons; LangmuirBlodgett lms; Nonlinear Schrdinger equation Further Reading
Bartnik, E.A., Blinowska, K.J. & Tuszy ski, J.A. 1992. Stability n of quantum capture in LangmuirBlodgett monolayers against positional disorder. Physics Letters A, 169: 4650 Christiansen, P.L., Gaididei, Yu.B., Johansson, M., Rasmussen, K.O., Mezentsev, V.K. & Rasmussen, J.J. 1998. Solitary excitations in discrete two-dimensional nonlinear Schrdinger models with dispersive dipole-dipole interactions. Physical Review B, 57: 11303 Czikkely, V., Dreizler, G., Frsterling, H., Kuhn, H., Sondermann, J., Tillmann, P. & Wiegand, J. 1969. Lichtabsorption von Farbstoff-Moleklpaaren in Sandwichsystemen aus monomolekularen Schichten. Zeitschrift fr Naturforschung, 24A: 1823 Czikkely, V., Frsterling, H. & Kuhn, H. 1970. Extended dipole model for aggregates of dye molecules. Chemical Physics Letters, 6: 207 Huth, G.C., Gutmann, F. & Vitiello, G. 1989. Ring solitonic vibrations in schiebe aggregates. Physics Letters A, 140: 339 Inoue, T. 1985. Optical absorption and luminescence in Langmuir lms of merocyanine dye. Thin Solid Films, 132: 21 Jelly, E.E. 1936. Spectral absorption and uorescence of dyes in the molecular state. Nature, 138: 10091010 Knapp, E.W. 1984. Lineshapes of molecular aggregates exchange narrowing and intersite correlation. Chemical Physics, 85: 73 Kuhn, H. 1979. Synthetic molecular organizates. Journal of Photochemistry, 10: 111 Moebius, D. 1989. Monolayer assemblies. Berichte der BunsenGesellschaftPhysical Chemistry, 82: 848 Moebius, D. & Kuhn, H. 1988. Energy transfer in monolayers with cyanine dye Scheibe aggregates. Journal of Applied Physics, 64: 51385141 Scheibe, G. 1936. Variability of the absorption spectra of some sensitizing dyes and its cause. Angewandte Chemie, 49: 567 Spano, F.C., Kuklinski, J.R. & Mukamel, S. 1990. Temperature dependent superradiant decay of excitons in small aggregates. Physical Review Letters, 65: 211 Tuszy ski, J.A., Joergensen, M.F. & Moebius, D. 1999. n Mechanisms of exciton energy transfer in Scheibe aggregates. Physical Review E, 59: 4374

hyphen

Manuscript Queries

Title: Encyclopedia of Non-linear Sciences Alphabet S: Scheibe aggregates

Page 1

Query Number 1

Query Moebius 1978 or 1989, Please confirm