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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 3279-3284 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: To study the localization of Frenkel excitons in binary systems, we consider a model that has features both of the Anderson model (diagonal disorder characterized by a probability distribution of width w) and of the quantum percolation model (substitutional disorder characterized by an occupational probability p for one of the components). With a finite-size scaling (phenomenological renormalization group) technique, and the concept of quantum connectivity, we calculate the position of the phase boundary separating localized from extended states in the w–p disorder plane. At the two endpoints of the boundary, we find that for the Anderson model the critical disorder is wc=15.95±0.25, and for the quantum percolation model the localization threshold is pq=0.477±0.011.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 897-907 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The double proton transfer in benzoic acid crystals can be described by a double-minimum potential. At low temperatures one need consider only the two lowest energy eigenstates, which must be coupled to the crystalline phonons in order to obtain relaxation. Thus the benzoic acid system provides a well-defined chemical example of the spin–boson Hamiltonian. Within this model the tunneling relaxation between localized states occurs by one-phonon emission or absorption. Alternatively, at high temperatures the proton transfer is thermally activated. With this simple picture in mind we analyze NMR T1 relaxation experiments. The temperature-dependent proton transfer rate that emerges from the NMR analysis is in good agreement with inelastic neutron scattering experiments. Optical transitions of a dye probe have also been used to determine proton transfer rates in crystalline benzoic acid. Our model allows us to discuss both doped and pure crystal experiments within a unified framework. Thus, we find that all three different experimental probes yield results that are consistent with our simple theoretical picture. From our results we can determine the proton–phonon coupling constant.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 2703-2707 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In order to calculate the critical concentration for the metal–insulator transition in doped semiconductors, we study a model of randomly positioned interacting hydrogenic atoms within the one-electron approximation. We calculate approximate eigenfunctions for the system with the standard linear combination of atomic orbital variation method, considering explicitly the nonorthogonality of hydrogenic 1s orbitals. We then compute the correlation length using the concept of quantum connectivity, which we developed to study the localization transition in other disordered quantum-mechanical models. Finally, we employ a finite-size scaling analysis to determine the critical impurity concentration nc. If the isolated impurities have a Bohr radius a, then we find that Rc≡n1/3ca=0.250±0.011, which is in good agreement with experiment (Rc=0.26±0.05).
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 8-18 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The absorption spectrum of an optical transition of a dilute solute in a glassy or liquid solvent is usually inhomogeneously broadened. In a concentrated solution, the question arises as to whether or not the transition energy distributions of nearby solutes are correlated. Such correlation has important implications for coherent or incoherent transport and optical dephasing experiments. We present a molecular theory of this correlation. For a simple model of Lennard-Jones solutes in a Lennard-Jones liquid solvent, we compare our theory to Monte Carlo simulations, finding reasonable agreement. For a model with longer range solute–solvent interactions, where the excited state solute is ionized, the theory predicts very significant correlation effects. This suggests that for more realistic models with dipolar interactions, significant correlation effects will also be present.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 1775-1782 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider a quantum–mechanical two-level system under the influence of both diagonal and off-diagonal stochastic perturbations, and focus on the decay times T1 and T2, which refer to the relaxation to equilibrium of the populations and relative phase of the two levels, respectively. From both theoretical and experimental viewpoints one traditionally expects that T2≤2T1. On the other hand, from a fourth-order cumulant expansion calculation of the asymptotic time dependence of the density matrix elements, Budimir and Skinner [J. Stat. Phys. 49, 1029 (1987)] showed that, in fact, in some instances T2〉2T1. In this paper we solve the stochastic model numerically, which leads to the exact time dependence of the density matrix at all times. We find that the analytic prediction that T2〉2T1 is not only correct, but also meaningful, in the sense that the density matrix elements decay exponentially after only a short transient time.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 3880-3881 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 3274-3281 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Recently, Sesselmann et al. [Phys. Rev. B 36, 7601 (1987)] have examined the effect of pressure changes on hole-burning spectra of dye molecules in polymer glasses, finding that the hole shift and broadening are linear in the pressure change and its magnitude, respectively. We develop a statistical, microscopic theory of this effect, and of the inhomogeneous line shape itself. In the limit that the density of solvent perturbers becomes large, the general theory predicts that both the inhomogeneous line shape and the hole shape after a pressure change will be Gaussian, in qualitative agreement with experiment. By considering a specific model for the solute–solvent interaction, we then provide a quantitative analysis of the experiments that shows that the pressure broadening is due to changes in the local environment of each chromophore. As a further test of the theory, we make a prediction as to the frequency dependence of the pressure-dependent hole shift, which can be easily tested by experiment.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 6153-6159 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the classical and quantum percolation of spheres in a three-dimensional continuum. Each sphere has an impenetrable hard core of diameter σ, and two spheres are considered to be directly connected if the distance between their centers is less than d. We calculate the critical percolation density as a function of σ/d. In the classical problem this is the density ρc at which an infinite cluster of connected spheres first forms. In the quantum problem, we study a tight-binding model where the hopping matrix element between two spheres is nonzero only if they are directly connected. In this case the critical density ρq is the density at which the eigenstates of the Hamiltonian first become extended. Our method uses Monte Carlo simulation and finite-size scaling techniques, and for the quantum problem, the concept of quantum connectivity. We find that both ρc and ρq exhibit nonmonotonic behavior as a function of σ/d. We also find that for all values of σ/d, ρq〉ρc, although the ratio of the thresholds decreases with increasing σ/d. We argue that a better understanding of this ratio is obtained by considering the average coordination number. We speculate about the nature of both classical and quantum percolation as σ/d approaches 1.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 8973-8982 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We perform numerical calculations on a simple cubic lattice for a standard diagonally disordered tight-binding Hamiltonian, whose random site energies are chosen from a Gaussian distribution with variance ∑2. From phenomenological renormalization group studies of the localization length, we determine that the critical disorder is σc≡∑c/J=6.00±0.17, which is in good agreement with previous results (J is the nearest neighbor transfer matrix element). From our calculations we can also determine the mobility edge trajectory, which appears to be analytic at the band center. Defining an order parameter exponent β, which determines how the fraction of extended states vanishes as the critical point is approached from below, this implies that β=1/2, in agreement with a previous study. From a finite-size scaling analysis we find that π2/ν=1.43±0.10, where π2 and ν are the inverse participation ratio and localization length critical exponents, respectively. This ratio of exponents can also be interpreted as the fractal dimension (also called the correlation dimension) D2 of the critical wave functions. Generalizations of the inverse participation ratio lead to a whole set of critical exponents πk, and corresponding generalized fractal dimensions Dk=πk/ν(k−1). From finite-size scaling results we find that D3=1.08±0.10 and D4=0.87±0.09. The inequality of the three dimensions D2, D3, and D4 shows that the critical wave functions have a multifractal structure. Using a generalized phenomenological renormalization technique on the participation ratios, we find that ν=0.99±0.04. This result is in agreement with experiments on compensated or amorphous doped semiconductors.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 4391-4402 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Kubo's stochastic theory of the spectral line shape provides an elegant phenomenological description of inhomogeneous and homogeneous broadening and the transition between the two. This theory has been used profitably in the analysis of many experiments. In this paper we attempt to provide a microscopic foundation for the Kubo model by developing a completely molecular theory of the line shape. For definiteness we focus on the optical line shape of dilute chromophores in nonpolar fluids. Many of the features of the Kubo theory are found in the molecular theory; indeed, the molecular theory produces microscopic expressions involving the solvent structure and dynamics for Kubo's phenomenological parameters, and provides some justification for the Gaussian assumption in the stochastic theory. On the other hand, the molecular theory produces a transition frequency time-correlation function that is distinctly nonexponential, in contrast to the exponential assumption of the Kubo theory, and it is found that this nonexponentiality is necessary for the accurate description of line shapes in the regime intermediate between inhomogeneous and homogeneous broadening. For a model of Lennard-Jones particles the molecular theory is compared with molecular dynamics computer simulations.
    Type of Medium: Electronic Resource
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