Structural variability in transition metal oxide clusters: gas phase vibrational spectroscopy of V3O6-8+

We present gas phase vibrational spectra of the trinuclear vanadium oxide cations V3O6+[middle dot]He1-4{,} V3O7+[middle dot]Ar0{,}1{,} and V3O8+[middle dot]Ar0{,}2 between 350 and 1200 cm-1. Cluster structures are assigned based on a comparison of the experimental and simulated IR spectra. The latter are derived from B3LYP/TZVP calculations on energetically low-lying isomers identified in a rigorous search of the respective configurational space{,} using higher level calculations when necessary. V3O7+ has a cage-like structure of C3v symmetry. Removal or addition of an O-atom results in a substantial increase in the number of energetically low-lying structural isomers. V3O8+ also exhibits the cage motif{,} but with an O2 unit replacing one of the vanadyl oxygen atoms. A chain isomer is found to be most stable for V3O6+. The binding of the rare gas atoms to V3O6-8+ clusters is found to be strong{,} up to 55 kJ/mol for Ar{,} and markedly isomer-dependent{,} resulting in two interesting effects. First{,} for V3O7+[middle dot]Ar and V3O8+[middle dot]Ar an energetic reordering of the isomers compared to the bare ion is observed{,} making the ring motif the most stable one. Second{,} different isomers bind different number of rare gas atoms. We demonstrate how both effects can be exploited to isolate and assign the contributions from multiple isomers to the vibrational spectrum. The present results exemplify the structural variability of vanadium oxide clusters{,} in particular{,} the sensitivity of their structure on small perturbations in their environment

Conformational flexibility of mephenesin

The mephenesin molecule (3-(2-methylphenoxy)propane-1,2-diol) serves as a test bank to explore several structural and dynamical issues, such as conformational flexibility, the orientation of the carbon linear chain relative to the benzene plane, or the effect of substituent position on the rotational barrier of a methyl group. The molecule has been studied by rotational spectroscopy in the 4-18 GHz frequency range by Fourier-transform methods in a supersonic expansion. The experiment has been backed by a previous conformational search plus optimization of the lowest energy structures by ab initio and density functional quantum calculations. The three lowest-lying conformers that can interconvert to each other by simple bond rotations have been detected in the jet. Rotational parameters for all structures have been obtained, and methyl torsional barriers have been determined for the two lowest-lying rotamers. The lowest-lying structure of mephenesin is highly planar, with all carbon atoms lying nearly in the benzene ring plane, and is stabilized by the formation of cooperative intramolecular hydrogen bonding. An estimation of the relative abundance of the detected conformers indicates that the energetically most stable conformer will have an abundance near 80% at temperatures relevant for biological activity