A repulsive reference potential reproducing the dynamics of a liquid with attractions

A well-known result of liquid state theory is that the structure of dense fluids is mainly determined by repulsive forces. The WCA potential, which cuts intermolecular potentials at their minima, is therefore often used as a reference. However, this reference gives quite wrong results for the viscous dynamics of the Kob-Andersen binary Lennard-Jones liquid [Berthier and Tarjus, Phys. Rev. Lett. 103, 170601 (2009)]. We show that repulsive inverse-power law potentials provide a useful reference for this liquid by reproducing its structure, dynamics, and isochoric heat capacity

Cooperative Dynamics in Unentangled Polymer Fluids

We present a Generalized Langevin Equation for the dynamics of interacting semiflexible polymer chains, undergoing slow cooperative dynamics. The calculated Gaussian intermolecular center-of-mass and monomer potentials, wich enter the GLE, are in quantitative agreement with computer simulation data. The experimentally observed, short-time subdiffusive regime of the polymer mean-square displacements, emerges here from the competition between the intramolecular and the intermolecular mean-force potentials.Comment: 9 pages, latex, 3 figure

Feedback Effect on Landau-Zener-Stueckelberg Transitions in Magnetic Systems

We examine the effect of the dynamics of the internal magnetic field on the staircase magnetization curves observed in large-spin molecular magnets. We show that the size of the magnetization steps depends sensitively on the intermolecular interactions, even if these are very small compared to the intra-molecular couplings.Comment: 4 pages, 3 Postscript figures; paper reorganized, conclusions modifie

Simple Two-Dimensional Model for the Elastic Origin of Cooperativity among Spin States of Spin-Crossover Complexes

We study the origin of the cooperative nature of spin crossover (SC) between low spin (LS) and high spin (HS) states from the view point of elastic interactions among molecules. As the size of each molecule changes depending on its spin state, the elastic interaction among the lattice distortions provides the cooperative interaction of the spin states. We develop a simple model of SC with intra and intermolecular potentials which accounts for the elastic interaction including the effect of the inhomogeneity of the spin states, and apply constant temperature molecular dynamics based on the Nos\'e-Hoover formalism. We demonstrate that, with increase of the strength of the intermolecular interactions, the temperature dependence of the HS component changes from a gradual crossover to a first-order transition.Comment: 4 pages, 4 figure

Collective excitations in liquid DMSO : FIR spectrum, Low frequency vibrational density of states and ultrafast dipolar solvation dynamics

Valuable dynamical and structural information about neat liquid DMSO at ambient conditions can be obtained through study of low frequency vibrations in the far infrared (FIR), that is, terahertz regime. For DMSO, collective excitations as well as single molecule stretches and bends have been measured by different kinds of experiments such as OHD-RIKES and terahertz spectroscopy. In the present work we investigate the intermolecular vibrational spectrum of DMSO through three different computational techniques namely (i) the far-infra red spectrum obtained through Fourier transform of total dipole moment auto time correlation function, (ii) from Fourier transform of the translational and angular velocity time autocorrelation functions and a (iii) quenched normal mode analysis of the parent liquid at 300K. The three spectrum, although exhibit differences among each other, reveal similar features which are in good, semi-quantitative, agreement with experimental results. Study of participation ratio of the density of states obtained from normal mode analysis shows that the broad spectrum around 100 cm-1 involves collective oscillations of 300-400 molecules. Dipolar solvation dynamics exhibit ultrafast energy relaxation (dipolar solvation dynamics) with initial time correlation function around 140 fs which can be attributed to the coupling to the collective excitations. We compare properties of DMSO with those of water vis-a-vis the existence of the low frequency collective modes. Lastly, we find that the collective excitation spectrum exhibits strong temperature dependence.Comment: 24 pages,8 figure