Two-dimensional time-frequency ultrafast infrared vibrational echo spectroscopy

2D spectrally resolved ultrafast (<200 fs) IR vibrational echo experiments were performed on Rh(CO)(2)acac [(acetylacetonato)dicarbonylrhodium (I)]. The 2D spectra display features that reflect the 0-1 and 1-2 transitions and the combination band transition of the symmetric (S) and antisymmetric (A) CO stretching modes. Three oscillations in the data arise from the frequency difference between the S and A modes (quantum beats) and the S and A anharmonicities. A new explanation is given for these "anharmonic" oscillations. Calculations show that spectral resolution enables the 0-1 and 1-2 dephasing to be measured independently.     

Communication: regularizing binding energy distributions and thermodynamics of hydration: theory and application to water modeled with classical and ab initio simulations

The high-energy tail of the distribution of solute-solvent interaction energies is poorly characterized for condensed systems, but this tail region is of principal interest in determining the excess free energy of the solute. We introduce external fields centered on the solute to modulate the short-range repulsive interaction between the solute and solvent. This regularizes the binding energy distribution and makes it easy to calculate the free energy of the solute with the field. Together with the work done to apply the field in the presence and absence of the solute, we calculate the excess chemical potential of the solute. We present the formal development of this idea and apply it to study liquid water.     

Settling time bounds forM/G/1 queues

This paper addresses the question of how long it takes for anM/G/1 queue, starting empty, to approach steady state. A coupling technique is used to derive bounds on the variation distance between the distribution of number in the system at timet and its stationary distribution. The bounds are valid for allt. This research was supported in part by a grant from the AT&T Foundation and NSF grant DCR-8351757.     

Thermal expansion of alkali halides above 300°K

The lattice parameter of NaCl, KCl, KBr, RbCl, RbBr, RbI, CsCl, CsBr and CsI from room temperature to near melting temperature, and of LiF, NaF and KI from room temperature to near 750°K, are measured using high temperature X-ray diffractometry. An orthogonal polynomial of second order with least square error approximation is fitted to the lattice parameter versus temperature data to obtain the thermal expansion coefficient. The Grüneisen's parameter is calculated using the available data, and in five salts it is found to increase gradually with temperature.     

Neutron and proton diffusion in heavy-ion collisions

A statistical theory for the exchange of protons and neutrons in heavy-ion collisions is formulated and applied to recent data. No systematic deviations are observed which could be evidence for (additional) quantal effects in the $\text{N}\text{Z}$ equilibration.     

Incorporation of single-walled carbon nanotubes into ferrocene-modified linear polyethylenimine redox polymer films

In this study, we describe the effects of incorporating single-walled carbon nanotubes (SWNTs) into redox polymer-enzyme hydrogels. The hydrogels were constructed by combining the enzyme glucose oxidase with a redox polymer (Fc-C(6)-LPEI) in which ferrocene was attached to linear poly(ethylenimine) by a six-carbon spacer. Incorporation of SWNTs into these films changed their morphology and resulted in a significant increase in the enzymatic response at saturating glucose concentrations (3 mA/cm(2)) as compared to films without SWNTs (0.6 mA/cm(2)). Likewise, the sensitivity at 5 mM glucose was significantly increased in the presence of SWNTs (74 μA/cm(2)·mM) as compared to control films (26 μA/cm(2)·mM). We demonstrate that the increase in the electrochemical and enzymatic response of these films depends on the amount of SWNTs incorporated and the method of SWNT incorporation. Furthermore, we report that the presence of SWNTs in thick films allows for more of the ferrocene redox centers to become accessible. The high current densities of the hydrogels should allow for the construction of miniature biosensors and enzymatic biofuel cells.     

More efficient Brownian dynamics algorithms

We examine the relative efficiencies of three- algorithms for performing Brownian Dynamics simulations without many-body hydrodynamics. We compare the conventional Brownian Dynamics algorithm of Ermak (CBD), Smart Monte Carlo (SMC) which incorporates Boltzmann sampling into essentially a CBD procedure, and the Stochastic Runge Kutta (SRK) method. We show, using the repulsive potential φ(r) = ε(σ/r) ⁿ , where n = 36 and 72, that the SRK algorithm gives the most accurate short-time dynamics for the mean-square displacements. The SRK algorithm static and dynamical properties converge better with a reducing time step to the exact values, than those generated by the CBD algorithm; giving efficiency gains typically of a factor of 3–4. Both CBD and SMC have the incorrect sign for the first correction term to the mean square displacement in a time step, whereas the SRK algorithm gives essentially the exact solution to order Δt ², where Δt is the simulation time step. In fact, these correction terms are almost equal and opposite in sign. Expressions for these terms were derived in terms of the average interaction energy per particle. The force, shear and bulk stress autocorrelation functions were calculated. The average energy per particle and time correlation functions at short time have values in excess of the exact values, while the corresponding quantities for SRK are below this. This difference in behaviour can be traced back to the extent of compliance of the particle trajectories with the exact expansion of the Smoluchowski equation. The accuracy, at a given value of the time step, of the stochastic algorithms can significantly depend on the form of the interaction potential between particles. It is also demonstrated that the long time limits of various correlation functions are fairly insensitive to a particular scheme (SRK or CBD) used in the simulations. All the correlation functions have a stretched exponential region at intermediate to long times, and the values of the exponents on density and force law steepness have been determined.     

Quaternary Centers by Nickel‐Catalyzed Cross‐Coupling of Tertiary Carboxylic Acids and (Hetero)Aryl Zinc Reagents

This work bridges a gap in the cross‐coupling of aliphatic redox‐active esters with aryl zinc reagents. Previously limited to primary, secondary, and specialized tertiary centers, a new protocol has been devised to enable the coupling of general tertiary systems using nickel catalysis. The scope of this operationally simple method is broad, and it can be used to simplify the synthesis of medicinally relevant motifs bearing quaternary centers.     

Alpha chain states in 4N-nuclei

We review the experimental evidence for alpha chain states in 4N-nuclei. Bloch-Brink cranked cluster model calculations suggest that such states should exist in all light A=4N nuclei. Recently a strong resonance has been observed in the¹²C(¹²C,¹²C(O ₂ ⁺ ))¹²C(O ₂ ⁺ ) reaction at 33 MeV which has been taken as evidence of a 6-α chain state in²⁴Mg. The angular distributions show strong peaks at 90° due to the simultaneous excitation of several nearly degenerate resonances with a range of L-values. We review our analysis of these data and present the results of calculations for the widths of resonances in hyperdeformed nuclei. We demonstrate that such resonances may have relatively narrow widths despite their high excitation energies. We surmise that the 33 MeV resonance in¹²C+¹²C scattering has a chain state structure.