: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Numerical solutions of partial differential equations by the finite element method, by C. Johnson. Pp 278. £40 (hardback), £15 (paperback). 1988. ISBN 0-521-34514-6, 34758-0 (Cambridge University Press)

One difficulty in using ion mobility (IM) mass spectrometry (MS) to improve the specificity of peptide ion assignments is that IM separations are performed using a range of pressures, gas compositions, temperatures, and modes of separation, which makes it challenging to rapidly extract accurate shape parameters. We report collision cross section values (Ω) in both He and N2 gases for 113 peptide ions determined directly from drift times measured in a low-pressure, ambient temperature drift cell with radio-frequency (rf) ion confinement. These peptide ions have masses ranging from 231 to 2969 Da, ΩHe of 89–616 A2, and ΩN2 of 151–801 A2; thus, they are ideal for calibrating results from proteomics experiments. These results were used to quantify the errors associated with traveling-wave Ω measurements of peptide ions and the errors concomitant with using drift times measured in N2 gas to estimate ΩHe. More broadly, these results enable the rapid and accurate determination of calibrated Ω for peptide ions, w...

Ion mobility mass spectrometry of peptide ions: effects of drift gas and calibration strategies.

Rapid, sensitive, and selective detection of explosives such as 2,4,6-trinitrotoluene (TNT) and 2,4,6-trinitrophenol (TNP), especially using a facile paper sensor, is in high demand for homeland security and public safety. Although many strategies have been successfully developed for the detection of TNT, it is not easy to differentiate the influence from TNP. Also, few methods were demonstrated for the selective detection of TNP. In this work, via a facile and versatile method, 8-hydroxyquinoline aluminum (Alq3)-based bluish green fluorescent composite nanospheres were successfully synthesized through self-assembly under vigorous stirring and ultrasonic treatment. These polymer-coated nanocomposites are not only water-stable but also highly luminescent. Based on the dramatic and selective fluorescence quenching of the nanocomposites via adding TNP into the aqueous solution, a sensitive and robust platform was developed for visual detection of TNP in the mixture of nitroaromatics including TNT, 2,4-dinitr...

Highly Selective and Sensitive Fluorescent Paper Sensor for Nitroaromatic Explosive Detection

Functional Data Analysis With R And Matlab

Ion mobility spectrometry (IMS) has become the most widely used technology for trace explosives detection. A key task in designing IMS systems is to balance the explosives detection performance with size, weight, cost, and safety of the instrument. Commercial instruments are, by and large, equipped with radioactive 63Ni ionization sources which pose inherent problems for transportation, safety, and waste disposal regulation. An alternative to a radioactive source is a corona discharge ionization source, which offers the benefits of simplicity, stability, and sensitivity without the regulatory problems. An IMS system was designed and built based on modeling and simulation with the goal to achieve a lightweight modular design that offered high performance for the detection of trace explosives using a corona ionization source. Modeling and simulations were used to investigate design alternatives and optimize parameters. Simulated spectra were obtained for 2,4,6-trinitrotoluene (TNT) and cyclo-1,3,5-trimethyl...

Modular ion mobility spectrometer for explosives detection using corona ionization.

The effect of space charge on the performance of an Ion Mobility Spectrometry (IMS) system becomes more important as the system is made smaller. We use the SIMION software package with the Statistical Diffusion Simulation (SDS) module and SIMION’s new capability to solve the Poisson equation to study the effect of space charge on ion loss and resolving power in IMS systems. We consider IMS systems ranging in length from 50 mm to 150 mm and in diameter from 8.33 mm to 50 mm with a fixed electric field of 50 V/mm. We also examine a system with a length of 50 mm, a diameter of 16.7 mm, and an electric field of 16.7 V/mm. We assume that any charge density can be injected into the IMS system, and we have obtained expressions that predict the ion loss and resolving power of IMS systems as a function of input charge density and drift tube aspect ratio (length/diameter).

Effect of space charge on resolving power and ion loss in ion mobility spectrometry.

Accurately computing molecular Raman spectra would enable rapid development of inexpensive and extensive Raman libraries. This is especially beneficial for chemicals that are regulated, toxic, or otherwise difficult to handle. Numerous quantum mechanical methods have been developed that enable computation of Raman spectra. Here, we study the B3LYP exchange correlation functional with various combinations of basis sets, polarization functions, and diffuse functions to determine which combination best computes the Raman spectra for explosive and nonexplosive molecules. In comparing spectra, three metrics were utilized: the root mean square error, the earth mover's distance, and the weighted cross-correlation average. The earth mover's distance and weighted cross-correlation metrics are shown to have significantly greater power at detecting spectral similarities and differences than the root mean square error. Across all methods and molecules examined, B3LYP/6-311++G(d,p) was found to provide the best match between measured and computed Raman spectra. Spectra generated at the B3LYP/6-311++G(d,p) level were found to be accurate enough to correctly identify each molecule out of a set of measured molecular spectra.

Predicting Raman Spectra Using Density Functional Theory

Systems, methods and computer program products for the multi-modal detection of particles are described herein. An embodiment of the present invention is a particle detector that includes a first chamber wherein analyte particles are subjected to a first particle detection mechanism, and a second chamber coupled to the first chamber, wherein the analyte particles are subjected to a second particle detection mechanism, and wherein the detection characteristics of second particle detection mechanism are orthogonal to detection characteristics of the first particle detection mechanism. According to another embodiment, the present invention is a particle detection method including the steps of detecting presence of at least one predetermined particle type in an analyte particle sample using a first particle detection mechanism, and confirming the presence of the predetermined particle type in the analyte particle sample using a second particle detection mechanism, wherein detection characteristics of the second particle detection mechanism are orthogonal to detection characteristics of the first detection mechanism.

Samar K. Guharay

Papers

Modular ion mobility spectrometer for explosives detection using corona ionization.

Effect of space charge on resolving power and ion loss in ion mobility spectrometry.

Predicting Raman Spectra Using Density Functional Theory

Multi-modal particle detector

Analysis of non-stationary dynamics in the financial system