Derivation of class II force fields. VIII. Derivation of a general quantum mechanical force field for organic compounds

A class II valence force field covering a broad range of organic molecules has been derived employing ab initio quantum mechanical "observables." The procedure includes selecting representative molecules and molecular structures, and systematically sampling their energy surfaces as described by energies and energy first and second derivatives with respect to molecular deformations. In this article the procedure for fitting the force field parameters to these energies and energy derivatives is briefly reviewed. The application of the methodology to the derivation of a class II quantum mechanical force field (QMFF) for 32 organic functional groups is then described. A training set of 400 molecules spanning the 32 functional groups was used to parameterize the force field. The molecular families comprising the functional groups and, within each family, the torsional angles used to sample different conformers, are described. The number of stationary points (equilibria and transition states) for these molecules is given for each functional group. This set contains 1324 stationary structures, with 718 minimum energy structures and 606 transition states. The quality of the fit to the quantum data is gauged based on the deviations between the ab initio and force field energies and energy derivatives. The accuracy with which the QMFF reproduces the ab initio molecular bond lengths, bond angles, torsional angles, vibrational frequencies, and conformational energies is then given for each functional group. Consistently good accuracy is found for these computed properties for the various types of molecules. This demonstrates that the methodology is broadly applicable for the derivation of force field parameters across widely differing types of molecular structures. Copyright 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1782-1800, 2001     

A New Pulsed Flow Modulation GC × GC–MS with Cold EI System and Its Application for Jet Fuel Analysis

We designed and operated a new system of pulsed flow modulation (PFM) two dimensional comprehensive gas chromatography (GC × GC) mass spectrometry (MS). This system is based on the combination of PFM–GC × GC with a quadrupole mass spectrometer of GC–MS via a supersonic molecular beams interface and its fly-through Cold EI ion source and applied this system for the analysis of JP8 jet fuel. PFM is a simple GC × GC modulator that does not consume cryogenic gases while providing tunable second GC × GC column injection time for enabling the use of quadrupole based mass spectrometry regardless its limited scanning speed. We analyzed JP8 jet fuel with our new PFM–GC × GC–MS with Cold EI system and found that as the second dimension GC elution time is increased the observed molecular ion mass is reduced. This unique observation that helped in improved sample compounds identification under co-elution conditions was enabled via having abundant molecular ions in Cold EI for all the fuel compounds. We named this type of analysis as PFM–GC × GC × MS. We found and discuss in this paper that PFM–GC × GC–MS with Cold EI combines improved separation of GC × GC with Cold EI benefits of tailing-free ultra-fast ion source response time and enhanced molecular ions and mass spectral isomer and isotope information for the provision of increased sample identification information.

     

An empirical re-examination of natural resource scarcity and economic growth

This paper is concerned with the effect of natural resource scarcity on economic growth in the United States. After defining the notion of scarcity and introducing two measures of scarcity—unit costs and relative resource price—changes in resource scarcity trends for lead, zinc, nickel, aluminium, silver, iron and copper over the most recent three decades are investigated. Only for silver and iron is there any indication that such a change has occurred. For silver, the change is transitory. To the extent that change takes place, it has implications for future economic growth, i.e. natural resource scarcity and economic growth are interrelated. To see whether this is a relevant concern, subsequent to the examination of changing resource scarcity trends an objective effort is made to identify a long-run equilibrium relationship between natural resource scarcity and economic growth. Relying on cointegration techniques, only for the unit cost measure for lead and copper for one of the measures of cointegration is there a suggestion that natural resource scarcity has affected economic growth in the United States over the period 1889–1992.     

A Communication Multiplexer Problem: Two Alternating Queues with Dependent Randomly-Timed Gated Regime

Two random traffic streams are competing for the service time of a single server (multiplexer). The streams form two queues, primary (queue 1) and secondary (queue 0). The primary queue is served exhaustively, after which the server switches over to queue 0. The duration of time the server resides in the secondary queue is determined by the dynamic evolution in queue 1. If there is an arrival to queue 1 while the server is still working in queue 0, the latter is immediately gated, and the server completes service there only to the gated jobs, upon which it switches back to the primary queue. We formulate this system as a two-queue polling model with a single alternating server and with randomly-timed gated (RTG) service discipline in queue 0, where the timer there depends on the arrival stream to the primary queue. We derive Laplace–Stieltjes transforms and generating functions for various key variables and calculate numerous performance measures such as mean queue sizes at polling instants and at an arbitrary moment, mean busy period duration and mean cycle time length, expected number of messages transmitted during a busy period and mean waiting times. Finally, we present graphs of numerical results comparing the mean waiting times in the two queues as functions of the relative loads, showing the effect of the RTG regime.     

Size-dependent tunneling and optical spectroscopy of CdSe quantum rods

Photoluminescence excitation spectroscopy and scanning-tunneling spectroscopy are used to study the electronic states in CdSe quantum rods that manifest a transition from a zero-dimensional to a one-dimensional quantum-confined structure. Both optical and tunneling spectra show that the level structure depends primarily on the diameter of the rod and not its length. With increasing diameter, the band gap and the excited state level spacings shift to the red. The level structure was assigned using a multiband effective-mass model, showing a similar dependence on rod dimensions.     

A colorimetric method for the estimation of glutamic acid in protein hydrolyzates

On heating with hydroxylamine and on subsequent treatment with ferric chloride, pyrrolidonecarboxylic acid gives a colour reaction. This reaction can be used for the quantitative estimation of glutamic acid in protein hydrolyzates since this acid is almost completely converted into pyrrohdonecarboxylic acid at 125° and pH 3–4.