Toward high-performance computational chemistry: I. Scalable Fock matrix construction algorithms

Several parallel algorithms for Fock matrix construction are described. The algorithms calculate only the unique integrals, distribute the Fock and density matrices over the processors of a massively parallel computer, use blocking techniques to construct the distributed data structures, and use clustering techniques on each processor to maximize data reuse. Algorithms based on both square and row-blocked distributions of the Fock and density matrices are described and evaluated. Variants of the algorithms are discussed that use either triple-sort or canonical ordering of integrals, and dynamic or static task clustering schemes. The algorithms are shown to adapt to screening, with communication volume scaling down with computation costs. Modeling techniques are used to characterize algorithm performance. Given the characteristics of existing massively parallel computers, all the algorithms are shown to be highly efficient for problems of moderate size. The algorithms using the row-blocked data distribution are the most efficient. © 1996 by John Wiley & Sons, Inc.     

Low molecular weight organogelators derived from threefold symmetric tricarbamates

A group of new low molecular weight organogelators based on threefold symmetric tricarbamate were synthesized and characterized. The tricarbamates with long alkyl chains were able to gelate a wide range of polar and nonpolar organic solvents such as acetonitrile and cyclohexane, generally at concentrations lower than 20 g/L. The best organogel formation was obtained using a threefold symmetric tricarbamate in n-dodecane, in which a sufficiently transparent gel was formed at the critical gelation concentration 1 g/L. Intermolecular hydrogen bonding by the tricarbamate in a nonpolar solvent benzene-d₆ was indicated by ¹H NMR spectra. Its maximum UV absorption was 11 nm higher in chloroform than in n-dodecane, and this red shift indicated increased conjugation between the benzene core and the carbamate substituents, which confirmed a change in its conformation from nonpolar to polar solvent. The self-assembling behavior of the tricarbamate in dilute solutions was investigated by TEM. Fiber-like networks were observed in a large range of solution concentrations.     

Overexpression in Catharanthus roseus hairy roots of a truncated hamster 3-hydroxy-3-methylglutaryl-CoA reductase gene

Catharanthus roseus (L.) G. Don hairy roots harboring hamster 3-hydroxy-3-methylglutaryl-CoA reductase (HMGR) (EC 1.1.1.88) cDNA without membrane-binding domain were evaluated by quantifying the levels of sterols and some indol-alkaloids. Clone 236, with the highest hybridization signal, had the lowest soluble and microsomal HMGR activity and produced more ajmalicine and catharanthine than the control but had reduced campesterol concentration. Clone 19, with low hybridization signal, had high soluble HMGR activity and produced high levels of campesterol and five to seven times more serpentine than the control but a low level of ajmalicine and no accumulation of catharanthine. These results suggest a possible role for HMGR in indole alkaloid biosynthesis and a possible cosuppression of both the endogenous and foreign HMGR genes in clone 236.     

Accurate mass analysis of ethanesulfonic acid degradates of acetochlor and alachlor using high-performance liquid chromatography and time-of-flight mass spectrometry

Degradates of acetochlor and alachlor (ethanesulfonic acids, ESAs) were analyzed in both standards and in a groundwater sample using high-performance liquid chromatography-time-of-flight mass spectrometry with electrospray ionization. The negative pseudomolecular ion of the secondary amide of acetochlor ESA and alachlor ESA gave average masses of 256.0750+/-0.0049 amu and 270.0786+/-0.0064 amu respectively. Acetochlor and alachlor ESA gave similar masses of 314.1098+/-0.0061 amu and 314.1153+/-0.0048 amu; however, they could not be distinguished by accurate mass because they have the same empirical formula. On the other hand, they may be distinguished using positive-ion electrospray because of different fragmentation spectra, which did not occur using negative-ion electrospray.     

The Measurement of Ultrashort Light Pulses—Simple Devices,Complex Pulses

We review the state of the art of ultrashort-light-pulse measurement using frequency-resolved-optical-gating (FROG). Recent developments have extended the state of the art considerably. FROG devices for measuring the intensity and phase of ultrashort laser pulses have become so simple that almost no alignment is required. In addition, such devices not only operate single shot, but they also yield the two most important spatio-temporal distortions, spatial chirp and pulse-front tilt. With other FROG variations, it is now possible to measure more general ultrashort light pulses (i.e., pulses much more complex than common laser pulses), with time-bandwidth products as large as several thousand and as weak as a few hundred photons, and despite other difficulties such as random absolute phase and poor spatial coherence.     

Newton-Cotes integration for approximating Stieltjes (generalized Euler) constants

In the Laurent expansion

of the Riemann-Hurwitz zeta function, the coefficients are known as Stieltjes, or generalized Euler, constants. [When , (the Riemann zeta function), and .] We present a new approach to high-precision approximation of . Plots of our results reveal much structure in the growth of the generalized Euler constants. Our results when for , and when for (for such as 53/100, 1/2, etc.) suggest that published bounds on the growth of the Stieltjes constants can be much improved, and lead to several conjectures. Defining , we conjecture that is attained: for any given , for some (and similarly that, given and , is within of for infinitely many ). In addition we conjecture that satisfies for 1$">. We also conjecture that , a special case of a more general conjecture relating the values of and for . Finally, it is known that for . Using this to define for all real 0$">, we conjecture that for nonintegral , is precisely times the -th (Weyl) fractional derivative at of the entire function . We also conjecture that , now defined for all real arguments 0$">, is smooth. Our numerical method uses Newton-Cotes integration formulae for very high-degree interpolating polynomials; it differs in implementation from, but compares in error bounding to, Euler-Maclaurin summation based methods.

     

Halo structure of (14)Be

The two-neutron halo nucleus (14)Be has been investigated in a kinematically complete measurement of the fragments ((12)Be and neutrons) produced in dissociation at 35 MeV/nucleon on C and Pb targets. Two-neutron removal cross sections, neutron angular distributions, and invariant mass spectra were measured, and the contributions from electromagnetic dissociation (EMD) were deduced. Comparison with three-body model calculations suggests that the halo wave function contains a large nu(2s(1/2))(2) admixture. The EMD invariant mass spectrum exhibited enhanced strength near threshold consistent with a nonresonant soft-dipole excitation.