Photonic excitation models

Swift, J. L., Heuff, R. F. and Cramb, D. T. (2006) A two-photon excitation fluorescence cross-correlation assay for a model ligand-receptor binding system using quantum dots. Biophys. J., 90, 1396-1410. 

Sutherland RL, Brant MC, Heinrichs J, Rogers JE, Slagle JE, McLean DG, Fleitz PA (2005) Excited-state characterization and effective three-photon absorption model of two-photon-induced excited-state absorption in organic push-pull charge-transfer chromophores. J Opt... 

The measurements were carried out using polarized-light from synchrotron radiation. The angle-resolved UPS spectra were recorded for specific directions of photon incidence, photon polarization, and electron exit, chosen in order to resolve the momentum dependence of the 7t-electron energy bands which could be observed in this experiment. Details are available elsewhere63. The UPS results are analysed not only with the help of the valence effective Hamiltonian (VEH) method, but also with the help of new quantum-chemical calculations based upon the excitation model method64. The full VEH band structure is shown in Fig. 7.32. 

A typical problem of interest at Los Alamos is the solution of the infrared multiple photon excitation dynamics of sulfur hexafluoride. This very problem has been quite popular in the literature in the past few years. (7) The solution of this problem is modeled by a molecular Hamiltonian which explicitly treats the asymmetric stretch ladder of the molecule coupled implicitly to the other molecular degrees of freedom. (See Fig. 12.) We consider the the first seven vibrational states of the mode of SF (6v ) the octahedral symmetry of the SF molecule makes these vibrational levels degenerate, and coupling between vibrational and rotational motion splits these degeneracies slightly. Furthermore, there is a rotational manifold of states associated with each vibrational level. Even to describe the zeroth-order level states of this molecule is itself a fairly complicated problem. Now if we were to include collisions in our model of multiple photon excitation of SF, e wou d have to solve a matrix Bloch equation with a minimum of 84 x 84 elements. Clearly such a problem is beyond our current abilities, so in fact we neglect collisional effects in order to stay with a Schrodinger picture of the excitation dynamics. 

There are several other interesting topics in quantum optics which we would like to be able to study. For example, we would like model problems in double resonance spectroscopy, where there are two electromagnetic fields with possibly different polarizations simultaneously interacting with a molecule. This problem resembles the multiple photon excitation problem in that there is population migration along ladders of states, but in this case there can be a vastly larger number of quantum levels to treat — on the order of 2(2J+1). At room temperature, the most probable value of J for SF is about 60, which implies a 250 state calculation. 

Ru(bipy)3 + is the prototype of a very large family of MLCT species. In the standard model of the photoprocesses of this compound, a photon excites the molecule to an initial Frank-Condon singlet state, MLCT, that rapidly transforms to a triplet, MLCT, with a quantum yield of near unity. Femtosecond pump probe experiments have established a half-life of about 100 fs for the formation of the triplet state. Recent studies utilizing femtosecond time-resolved fluorescence emission spectroscopy has observed fluorescence emission from the Frank-Condon state itself and the hfetime of this state has been estimated to be 40 15 fs. ... 

This chapter is devoted to describe the impact of metallic nanosphere to the multi-photon excitation fluorescence of Tryptophan, and little further consideration to multi-photon absorption process will be given, as the reader can find several studies in [11-14]. In section II, the nonlinear light-matter interaction in composite materials is discussed through the mechanism of nonlinear susceptibilities. In section III, experimental results of fluorescence induced by multi-photon absorption in Tryptophan are reported and analyzed. Section IV described the main results of this chapter, which is the effect of metallic nanoparticles on the fluorescent emission of the Tryptophan excited by a multi-photon process. Influence of nanoparticle concentration on the Tryptophan-silver colloids is observed and discussed based coi a nonlinear generalization of the Maxwell Garnett model, introduced in section II. The main conclusion of the chapter is given in secticHi IV. 

Quantum chemical calculations essentially confirm the above simple model for the trans-cis isomerization of stilbene. Two-photon excitation spectra and more recent calculations indicate, however, that contrary to what is shown in Figure 7.3a, it is not the lowest but rather a higher excited A state of rra/i,v-stilbene that correlates with the lowest excited singlet state... 

A more direct evidence of the surface localized excitation mechanism has been obtained by a polarization dependence study. For K/Pt(lll) at 0.36 ML, it has been demonstrated that the coherent excitation of the K—Pt stretching mode occurs with p-polarized excitation and not with s-polarized exdtation. Since the s-polarization absorptance is about one fourth of that with p-polarization under the experimental conditions (2.19 eV photon energy, 70° angle of inddence), the coherent amplitude should be detectable with s-polarization if the substrate-mediated process operates. Therefore, the negligible oscillatory component with s-polarization is inconsistent with the substrate-mediated excitation model and it is indicated that some electronic transitions involving K-induced surface states are responsible for the coherent excitations. 

The model (9.73)—(9.75) was presented as an initial value problem We were interested in the rate at which a system in state 0) decays into the continua L and R and have used the steady-state analysis as a trick. The same approach can be more directly applied to genuine steady state processes such as energy resolved (also referred to as continuous wave ) absorption and scattering. Consider, for example, the absorption lineshape problem defined by Fig. 9.4. We may identify state 0) as the photon-dressed ground state, state 1) as a zero-photon excited state and the continua R and L with the radiative and nonradiative decay channels, respectively. The interactions Fyo and correspond to radiative (e.g. dipole) coupling elements between the zero photon excited state 11 and the ground state (or other lower molecular states) dressed by one photon. The radiative quantum yield is given by the flux ratio Yr = Jq r/(Jq r Jq l) = Tis/(Fijj -F F1/,). 

In this case, the second-order hyperpolarizability y can be considered as a unidimensional parameter defined along the axis x of the molecule following the single component Yxxxx- Equation 3 can be simpUfied into the relationship Eq. 5, when applying the three-level model in which the lowest excited state 11) and the two-photon excited state 2) are considered to be the most significant... 

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