Chemistry. Beyond platonic molecules

Molecular motion is influenced by quantum mechanics, which thus affect molecular properties such as their reactivity and the ease with which they isomerize. In his Perspective, Bowman describes recent theoretical advances that allow accurate quantum mechanical calculation of molecular motions for ever larger systems.     

Internal rotation and spin conversion of CH3OH in solid para-hydrogen

The quantum solid para-hydrogen (p-H2) has recently proven useful in matrix isolation spectroscopy. Spectral lines of compounds embedded in this host are unusually narrow, and several species have been reported to rotate in p-H2. We found that a p-H2 matrix inhibits rotation of isolated methanol (CH3OH) but still allows internal rotation about the C-O bond, with splittings of the E/A torsional doublet in internal rotation-coupled vibrational modes that are qualitatively consistent with those for CH3OH in the gaseous phase. This simplified high-resolution spectrum further revealed the slow conversion of nuclear spin symmetry from species E to species A in the host matrix, offering potential insight into nuclear spin conversion in astrophysical sources.     

Separation and conversion dynamics of four nuclear spin isomers of ethylene

Molecules with three or more nuclei of nonzero spin exist as discrete spin isomers whose interconversion in the gas phase is generally considered improbable. We have studied the interconversion process in ethylene by creating a sample depleted in the B2u nuclear spin isomer. The separation was achieved through spatial drift of this isomer induced by resonant absorption of narrow-band infrared light. Evolution of the depleted sample revealed conversion between B2u and B3u isomers at a rate linearly proportional to pressure, with a rate constant of 5.5 (+/-0.8) x 10(-4) s(-1) torr(-1). However, almost no change was observed in the Ag isomer populations. The results suggest a spin conversion mechanism in C2H4 via quantum relaxation within the same inversion symmetry.