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Ab initio calculations of torsionally mediated hyperfine splittings in E states of acetaldehyde.

ABSTRACT: Quantum chemistry packages can be used to predict with reasonable accuracy spin-rotation hyperfine interaction constants for methanol, which contains one methyl-top internal rotor. In this work we use one of these packages to calculate components of the spin-rotation interaction tensor for acetaldehyde. We then use torsion-rotation wavefunctions obtained from a fit to the acetaldehyde torsion-rotation spectrum to calculate the expected magnitude of hyperfine splittings analogous to those observed at relatively high J values in the E symmetry states of methanol. We find that theory does indeed predict doublet splittings at moderate J values in the acetaldehyde torsion-rotation spectrum, which closely resemble those seen in methanol, but that the factor of three decrease in hyperfine spin-rotation constants compared to methanol puts the largest of the acetaldehyde splittings a factor of two below presently available Lamb-dip resolution.

SUBMITTER: Xu LH

PROVIDER: S-EPMC6508553 | biostudies-literature | 2017

REPOSITORIES: biostudies-literature

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Ab initio calculations of torsionally mediated hyperfine splittings in E states of acetaldehyde.

Xu Li-Hong LH Reid E M EM Guislain B B Hougen J T JT Alekseev E A EA Krapivin I I

Journal of molecular spectroscopy 20170101

Quantum chemistry packages can be used to predict with reasonable accuracy spin-rotation hyperfine interaction constants for methanol, which contains one methyl-top internal rotor. In this work we use one of these packages to calculate components of the spin-rotation interaction tensor for acetaldehyde. We then use torsion-rotation wavefunctions obtained from a fit to the acetaldehyde torsion-rotation spectrum to calculate the expected magnitude of hyperfine splittings analogous to those observe ...[more]

PMID: 31080294

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