A classical dynamics method for H2 diffraction from metal surfaces

We present a discretization method that allows one to interpret measurements on diffraction of diatomic molecules from solid surfaces using six-dimensional (6D) classical trajectory calculations. It has been applied to the D2NiAl(110) and H2Pd(111) systems (which are models for activated and nonactivated dissociative chemisorption, respectively) using realistic potential energy surfaces obtained from first principles. Comparisons with experimental results and 6D quantum dynamical calculations show that, in general, the method is able to predict the relative intensity of the most important diffraction peaks. We therefore conclude that classical mechanics can be an efficient guide for experimentalists in the search for the most significant diffraction channels.     

EFFECT OF THE PHYSICAL STATE OF PHOSPHOLIPID ON RHODOPSIN REGENERATION FROM RETINYLIDENE PHOSPHOLIPID

Abstract— Rhodopsin regeneration in rod membranes involves reactions of all -trans retinal (released from bleached pigment) with phosphatidylethanolamine, photic isomerization of retinal, and binding of 11-cis retinal to opsin. This investigation demonstrated that formation of retinylidene phospholipid and retinal binding to opsin were both affected by the physical state of phospholipid. A fluid membraneous environment provided by the acyl chains of phospholipid was essential for these reactions to proceed efficiently. The retinal moiety of retinylidene phospholipid appeared to be directly transferred to opsin by transimination.     

Oligodeoxynucleotides Containing 2′‐Deoxy‐1‐methyladenosine and Dimroth Rearrangement

2′‐Deoxy‐1‐methyladenosine was incorporated into synthetic oligonucleotides by phosphoramidite chemistry. Chloroacetyl protecting group and controlled anhydrous deprotection conditions were used to avoid Dimroth rearrangement. Hybridization studies of intramolecular duplexes showed that introduction of a modified residue into the loop region of the oligonucleotide hairpin increases the melting temperature. It was shown that modified oligonucleotides may be easily transformed into oligonucleotides containing 2′‐deoxy‐N⁶‐methyladenosine.     

Syntheses, structure, and selected physical properties of CsLnMnSe3 (Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y) and AYbZnQ3 (A = Rb, Cs; Q = S, Se, Te)

CsLnMnSe(3) (Ln = Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Y) and AYbZnQ(3) (A = Rb, Cs; Q = S, Se, Te) have been synthesized from solid-state reactions at temperatures in excess 1173 K. These isostructural materials crystallize in the layered KZrCuS(3) structure type in the orthorhombic space group Cmcm. The structure is composed of LnQ(6) octahedra and MQ(4) tetrahedra that share edges to form [LnMQ(3)] layers. These layers stack perpendicular to [010] and are separated by layers of face- and edge-sharing AQ(8) bicapped trigonal prisms. There are no Q-Q bonds in the structure of the ALnMQ(3) compounds so the formal oxidation states of A/Ln/M/Q are 1+/3+/2+/2-. The CsLnMnSe(3) materials, with the exception of CsYbMnSe(3), are Curie-Weiss paramagnets between 5 and 300 K. The magnetic susceptibility data for CsYbZnS(3), RbYbZnSe(3), and CsYbMSe(3) (M = Mn, Zn) show a weak cusp at approximately 10 K and pronounced differences between field-cooled and zero-field-cooled data. However, CsYbZnSe(3) is not an antiferromagnet because a neutron diffraction study indicates that CsYbZnSe(3) shows neither long-range magnetic ordering nor a phase change between 4 and 295 K. Nor is the compound a spin glass because the transition at 10 K does not depend on ac frequency. The optical band gaps of the (010) and (001) crystal faces for CsYbMnSe(3) are 1.60 and 1.59 eV, respectively; the optical band of the (010) crystal faces for CsYbZnS(3) and RbYbZnSe(3) are 2.61 and 2.07 eV, respectively.     

Self-chemical ionization of diethylzinc

The self-chemical ionization of diethylzinc is examined by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and semiempirical molecular orbital calculations. Electron impact of diethylzinc neutral produces the radical cation, C(4)H(15)Zn(+) (m/z x 122), which reacts further with the neutral (C(2)H(5))(2)Zn to give the following product ions: Zn(+) (m/z x 64), C(2)H(5)Zn(+) (m/z x 93), C(4)H(9)Zn(+) (m/z x 121), C(4)H(11)Zn(2)(+) (m/z x 187), and C(6)H(15)Zn(2)(+) (m/z x 215). To determine the structure and pathways for production of these ions, monoisotopic (12)C(4)H(15)(64)Zn(+), (64)Zn(+) and (12)C(2)H(5)(64)Zn(+) were individually isolated and reacted with the neutral background. We also performed semiempirical molecular orbital calculations (ZINDO/1). The molecular orbital calculations and experimental data are consistent in predicting that the ethyl group on the diethylzinc cation carries the positive charge. Copyright 1999 John Wiley & Sons, Ltd.     

Relaxation and transport in FCHC lattice gases

FCHC lattice gases are the basic models for studying flow problems in three-dimensional systems. This paper presents a self-contained theoretical analysis and some computer simulations of such lattice gases, extended to include an arbitrary number of rest particles, with special emphasis on non-semi-detailed balance (NSDB) models. The special FCHC lattice symmetry guarantees isotropy of the Navier-Stokes equations, and enumerates the 12 spurious conservation laws (staggered momenta). The kinetic theory is based on the mean field approximation or the nonlinear Boltzmann equation. It is shown how calculation of the eigenvalues of the linearized Boltzmann equation offers a simple alternative to the Chapman-Enskog method or the multi-time-scale methods for calculating transport coefficients and relaxation rates. The simulated values for the speed of sound in NSDB models slightly disagree with the Boltzmann prediction.     

Investigation of the Livengood–Wu integral for modelling autoignition in a high-pressure bomb

The reaction progress variable, which is widely used in premixed and diffusion combustion studies, comprises a set of pre-selected intermediate species to denote reaction progress. Progress towards autoignition can also be traced by the Livengood–Wu (LW) integral. Autoignition occurs when the LW integral attains a value of unity. This concept is further explored by applying it to an inhomogeneous mixture scenario, to determine the time and place of autoignition occurrence. A semidetailed mechanism (137 species and 633 reactions) for n-heptane/iso-octane/toluene is used in this study. Two numerical schemes based on the LW integral are proposed and incorporated into a computational fluid dynamics platform, to model autoignition in a 3D configuration, when a spray is injected into a constant volume bomb under diesel engine conditions. Tabulated chemistry, a traditional method of modelling autoignition using information from pre-calculated igniting diffusion flames, is also used for comparison purposes. The associated predicted pressure profiles are compared with experimental measurements.     

Direct simulation of fluid flow with cellular automata and the lattice-Boltzmann equation

With the invention of the Hexagonal Lattice Gas it was hoped that this new technique would facilitate direct simulation of turbulent flow. In the past years, however, we have learned about its barriers on numerical accuracy and computational efficiency, which cannot easily be taken. The work on lattice gases has evolved in the introduction of the lattice-Boltzmann scheme. With the appropriate refinements this scheme provides the essential balance between robustness and numerical accuracy and enables us to simulate three-dimensional time-dependent flows at Reynolds numbers up to 50000.     

Binary fluids in planar nanopores: Adsorptive selectivity, heat capacity and self-diffusivity

Monte Carlo and molecular dynamics simulations are performed to study fluid adsorption of a two component fluid in slit pores of nanoscopic dimensions. The slit pores are immersed in a binary fluid bath, which is comprised of spherical molecules having a size ratio of 1.43, at constant temperature and composition. Pore width is varied to determine how the heat capacity and self-diffusion coefficient are linked to the composition and structure of the adsorbed fluid. In pores where the fluid structure is most pronounced, we observe: perfect (or near perfect) exclusion of one component by the other component, a heat capacity that rapidly oscillates and is of greater magnitude than in the fluid bath, and self-diffusion coefficients on the order of 10^–8 cm²/s. The behavior of the heat capacity and diffusion coefficients appears to arise from a near solid-like layering of OMCTS that occurs at certain favorable pore widths.