A mass-selective ion transfer line coupled with a uniform supersonic flow for studying ion-molecule reactions at low temperatures.

A new approach based on the uniform supersonic flow technique-a cold, thermalized de Laval expansion offering the advantage of performing experiments with condensable species-has been developed to study ion-molecule reactions at low temperatures. It employs a mass-selective radio frequency transfer line to capture and select ions from an adaptable ionization source and to inject the selected ions in the core of the supersonic expansion where rate coefficients and product branching can be measured from room temperature down to ∼15 K. The transfer line incorporates segmented ion guides combining quadrupolar and octapolar field orders to maximize transmission through the differential apertures and the large pressure gradients encountered between the ionization source (∼mbar), the quadrupole mass filter (∼10-5 mbar), and the de Laval expansion (∼mbar). All components were designed to enable the injection of cations and anions of virtually any m/z ratio up to 200 at near ground potential, allowing for a precise control over the momentum and thermalization of the ions in the flow. The kinetics and branching ratios of a selection of reactions have been examined to validate the approach. The technique will be instrumental in providing new insight on the reactivity of polyatomic ions and molecular cluster ions in astrophysical and planetary environments.

Molecular dynamics simulations of anharmonic infrared spectra of [SiPAH](+) pi-complexes.

This paper presents an investigation of anharmonic effects in the IR spectra of [SiPAH](+) complexes by using Born-Oppenheimer molecular dynamics for a variety of PAHs ranging from naphthalene (C(10)H(8)) to ovalene (C(32)H(14)). The potential energy surfaces are calculated with the self-consistent charge density functional-based tight binding approach (DFTB). The DFTB parameters are modified to reproduce potential energy surfaces and the harmonic infrared spectra of the studied complexes with respect to DFT calculations. For bare PAHs, we find that the evolution of the vibrational frequencies of the C-H out-of-plane bending and C-C stretching modes as a function of temperature follows a linear law in quantitative agreement with experimental data. For cationic PAHs, the anharmonicity of the bands in terms of position shifts is found to be enhanced with respect to that of neutrals. As compared with bare cationic PAHs, the coordination of Si induces (i) larger broadenings, (ii) a slightly larger shift of the C-C stretching mode, and (iii) a smaller shift of the C-H out-of-plane bending modes. We discuss the implications of the work and the spectroscopic constraints for the detection of [SiPAH](+) in the interstellar medium.