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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. 1681-1694 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Grassberger–Procaccia method has been employed to study the transitions which occur as a classical Ar3 cluster, modeled by pairwise Lennard-Jones potentials, passes from a rigid, solid-like form to a nonrigid, liquid-like form with increasing energy. Power spectra and lower bounds on the fractal dimensions and K entropies are presented at several energies along the caloric curve for the Ar3 cluster. In addition, the full spectrum of Liapunov exponents has been computed at these same energies to get an accurate value of the K entropy. Chaotic behavior, though relatively small, is observed even at low energies where the power spectrum displays largely normal-mode structure. The degree of chaotic behavior increases with energy at energies where some degree of regularity is observed in the spectrum. However, at energies that just allow the system to pass into and across saddle regions separating local potential minima, the phase space appears to be separable into a region within the equilateral triangle potential well where the behavior is highly chaotic, and a region of lower dimensions and less chaos around the saddle of the linear configuration. Dimensions from approximately three to eight are observed. A clear separability of time scales for establishment of different extents of ergodicity permits the determination of fractal dimensions of the manifold on which the phase points moves, for time scales of physical, i.e., observable significance. We believe this to be the first evaluation of the dimensionality of the space on which the phase point moves, for a Hamiltonian system displaying this range of dimensions.
    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 94 (1991), S. 1584-1591 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We perform numerical simulations on a model of DNA molecules during gel electrophoresis in which the effect of periodically changing the applied field by 90° is examined. A random gel is used in this simulation. We find a scaling relationship between mobility and the ratio of the chain length to pulse time for 100 and 200 link chains. Also presented are results for the orientation, with respect to the new field direction, of chains being subjected to periodically varying orthogonal fields. We find no overshoot in this orientation. Results supporting the existence of persistence in the orientation of a chain over several field changes is presented for 400 link chains.
    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 93 (1990), S. 1347-1357 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Classical dynamical studies are presented of melting and diffusive behavior in the Ar13 cluster. A comparison is made between the standard Einstein form for the diffusion constant (and the equivalent Green–Kubo form) and a recently developed theory for dynamics and diffusion in liquids based on the dynamical Hessian matrix. Comparisons are also made to similar calculations on melting in bulk argon systems. In the molecular dynamics calculations, it is found that the onset of liquidlike behavior occurs rather suddenly across the transition region. Well-defined Fick's Law diffusive behavior occurs in liquidlike clusters over time scales long relative to the characteristic vibrational period. In studies involving the dynamical matrix, the distributions and numbers of positive and negative eigenvalues of the Hessian matrix are monitored as a function of energy and temperature, and the Einstein frequency of the cluster is computed.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5753-5763 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a numerically exact procedure for the calculation of an important class of finite temperature quantum mechanical time correlation functions. The present approach is based around the stationary phase Monte Carlo (SPMC) method, a general mathematical tool for the calculation of high dimensional averages of oscillatory integrands. In the present context the method makes possible the direct numerical path integral calculation of real-time quantum dynamical quantities for times appreciably greater than the thermal time (β(h-dash-bar)). Illustrative applications involving finite temperature anharmonic motion are presented. Issues of importance with respect to future applications are identified and discussed.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 3910-3922 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Extensive classical simulations of the melting–freezing transition of small clusters (N=7–33) of rare gas atoms have been performed in which quenching by steepest descent has been coupled to isoergic molecular dynamics. A mechanistic description of the phase change is given in terms of the local potential minima accessed in the transition region and the isomerization pathways for and the frequencies of interwell passages. All of the small clusters, at energies low in the transition range of energy, exhibit some separation (by factors of approximately 5 to 60) of the short time scale for motions about the various potential minima and the longer time scale separating interwell passages. The onset of diffusion is marked by passages over saddles linking the minima. Fully liquid-like behavior is observed for all the clusters when the time scale separation for the motions no longer exists. The coexistence and magic number phenomena observed in previous simulations are explained in terms of the kinds of potential minima on the surface and the accessibility of one from another. The existence of a potential energy minimum very low relative to the nearest accessible, high-lying minima as well as time scale separation are necessary conditions for the observation of the kind of coexistence of liquid-like and solid-like forms over a well-defined energy or temperature range predicted by a quantum statistical model and observed, e.g., in isoergic and isothermal simulations of the Ar13 cluster. Such conditions are met in some but not all clusters. Structures with underlying pentagonal, and especially icosahedral, symmetry are important for clusters in the size range N=7–33, not only in previously recognized cases; defective icosahedral structures occur among the lower-energy minima even for some clusters for which they had not been considered.
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  • 6
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A new method for studying the generation and structure of carbon cluster ions is described. A rotating, translating carbon rod is subjected to the focused output of an excimer laser operating at 308 nm. The resulting plume is directly sampled by a high resolution reverse geometry mass spectrometer operating between 2 and 8 kV. In this paper we report initial results for the positive cluster ions up to n=60. The mass spectra are bimodal with a minimum occurring between C+26 and C+31 in agreement with findings of other workers using related techniques. Metastable neutral loss is observed for all cluster ions with n≥5. Below C+30 the most intense neutral loss is C3 but intense C1 and C5 loss is observed for a significant number of systems and C10 and C14 for a few systems. Above C+30 the metastable loss spectra dramatically change and only C2, and a minor amount of C4 loss, is observed. The C+60 ion is slightly enhanced in the mass spectrum but its metastable reactivity is no different than any of the other C+n ions above n=30. The detailed results are interpreted in terms of stable structures of both the parent ions and neutral fragments that have been predicted theoretically.
    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 87 (1987), S. 545-554 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Simulations by constant energy molecular dynamics have been performed for numerous clusters in the size range N=7–33. Detailed investigations have been conducted on the portions of the caloric curves in which the transition between rigid and nonrigid behavior occurs, to study the N dependence of the solid–liquid phase change. Clusters of several sizes display a coexistence of forms, each with a characteristic mean temperature, over a well-defined energy range in the transition region, as had been observed for the Ar13 cluster. Within the coexistence region, the high temperature form is solid-like and the low temperature form behaves in a liquid-like fashion. The caloric curves of state for these clusters take on two-valued forms when averages are calculated for each of the two "phases'' separately; the two branches are smooth extensions of the curves from the single phase regions. Clusters of other sizes do not display this clear coexistence of phases, but appear to pass through a "slush-like'' state during the melting transition. The coexistence behavior is not a smooth function of N. The clusters Ar13 and Ar19, and to a certain extent Ar7, display high stability properties indicative of magic number behavior.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 3181-3191 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A method is presented for determining the stationary phase points for multidimensional path integrals employed in the calculation of finite-temperature quantum time correlation functions. The method can be used to locate stationary paths at any physical time; in the case that t(very-much-greater-than)β(h-dash-bar), the stationary points are the classical paths linking two points in configuration space. Both steepest descent and simulated annealing procedures are utilized to search for extrema in the action functional. Only the first derivatives of the action functional are required. Examples are presented first of the harmonic oscillator for which the analytical solution is known, and then for anharmonic systems, where multiple stationary phase points exist. Suggestions for Monte Carlo sampling strategies utilizing the stationary points are made. The existence of many and closely spaced stationary paths as well as caustics presents no special problems. The method is applicable to a range of problems involving functional integration, where optimal paths linking two end points are desired.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 5651-5656 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present here prototype studies of the effects of quantum mechanics on the melting of clusters. Using equilibrium path integral methods, we examine the melting transition for small rare gas clusters. Argon and neon clusters are considered. We find the quantum-mechanical effects on the melting and coexistence properties of small neon clusters to be appreciable.
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 116 (2002), S. 3277-3285 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A model of the polarizability of carbon disulfide dimers was constructed, using polarizabilities from accurate time-dependent density functional theory calculations as reference. This direct reaction field model takes dipole-induced dipole effects, induced multipole effects and effects due to the overlap of the electronic clouds into account in an approximate way. The importance of the induced multipole and the overlap effects is investigated. This polarizability model is subsequently used to calculate the third-order time-domain Raman response of liquid carbon disulfide. These results are compared to experimental data and earlier calculated response in which only dipole-induced dipole effects on the polarizability were included. The multipole effects are found to give a significant contribution to the subpico second part of the third-order Raman response. © 2002 American Institute of Physics.
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