Accurate equilibrium structures of methyl methacrylate and methacrylic acid by microwave spectroscopy and dispersion corrected calculations.

The rotational constants of s-trans and s-cis methyl methacrylate and methacrylic acid are determined from microwave spectra. All singly substituted heavy-atom isotopologs of the four species are measured in natural abundance. The experimental rotational constants are combined with anharmonic vibrational corrections using the Coulomb-attenuating method, Becke, three-parameter, Lee-Yang-Parr density functional with Grimme's D3 dispersion corrections and the Becke-Johnson damping function, yielding precise semi-experimental equilibrium rotational constants. These constants are used to determine semi-experimental equilibrium structures with sub-picometer accuracy, suitable for benchmarking purposes.

Blurring out hydrogen: The dynamical structure of teflic acid.

The microwave spectra of 10 teflic acid isotopologues were recorded in the frequency range of 3-25 GHz using supersonic jet-expansion Fourier transform microwave spectroscopy. Despite being asymmetric in its equilibrium structure, the delocalization of the hydrogen atom leads to a symmetric top vibrational ground state structure. In this work, we present the zero point structure obtained from the experimental rotational constants and an approach to determine the semi-experimental equilibrium structure aided by ab initio data. The Te-O bond length determined in the equilibrium structure is accurate to the picometer and can be used as a benchmark for computational methods treating relativistic effects.

Merging two molecular beams of ND3 up to the Liouville limit.

In low-energy collisions between two dipolar molecules, the long-range dipole-dipole interaction plays an important role in the scattering dynamics. Merged beam configurations offer the lowest collision energies achievable, but they generally cannot be applied to most dipole-dipole systems as the electrodes used to merge one beam would deflect the other. This paper covers the design and implementation of a merged electrostatic guide whose geometry was numerically optimized for ND3-ND3 and ND3-NH3 collisions. This device guides both beams simultaneously and makes them converge up to an effective collision angle of 2°, yielding the optimal compromise between spatial overlap and the lowest possible collision energy. We present preliminary data for inelastic ND3-ND3 collisions.