Anomalous Zeeman Splitting in the Rovibrational Spectrum of

Anomalous Zeeman Splitting in the Rovibrational Spectrum of the OH Radical Solvated in Superfluid Helium or: How I Learned to Stop Worrying and Love the Proverbial Droplet Effects ISMS 2019 Gary E. Douberly Department of Chemistry, University of Georgia Athens, Georgia, USA

Journal of Physical Chemistry A, (2013), 117, 8103 -8110 ~500% increase for OH (2 3/2)

-doubling Gas - interaction in the rotating molecule that leads to a slight L-uncoupling: Rotational levels are parity doubled. -Doublet Splitting, (sum of v=0 and v=1 -doubling) Increased by about (x 5) ∆ fe = 0. 29 cm-1 Gas Phase Helium droplet E (cm-1) Weff*m v=0 0. 0556 2. 4326 0. 198(3) 2. 358(23) v=1 0. 0513 2. 4463 0. 369(2) 2. 363(23)

A′′ A′ CCSD(T)/aug-cc-p. VTZ for H, O, F aug-cc-p. VQZ for He Orsay-Trento Functional / He-DFT

S-uncoupling and L-uncoupling matrix elements from Bob Field’s Spectra of Diatomic Molecules. Helium is assumed to have no effect on the fundamental interactions that lead to -doubling in the gas phase. e/f matrices have slightly different Bv constants.

Bvf % reduction OHb 0% Gas Phase 0. 5% 1. 5% E (J=3/2) 0. 0556 0. 0640 0. 227 E (J=3/2) 0. 0513 0. 0579 0. 418 0. 417 E (J=5/2) 0. 187 0. 211 1. 60 Be %diff (v=0) - 0 0. 61 Be %diff (v=1) - 0 1. 38 1. 44 (Av gas) 80. 80 gas , then 80. 79(1 e. g. if B 0 f = 0. 995*B 0 (exp) -139. 73 If. He – Ie. He = 10 -3 amu-Å2 -145 79. 12 - B 0 e 79. 87 /B 0 f) = 0. 0061 -170 -200 Anomalous -doubling due to parity dependent rotational energy level shifts upon solvation of OH in liquid helium.

OH Detect laserinduced depletion of ionization crosssection 1 Tesla Rare Earth Permanent Magnets (iron caps) BZ Elaser M = 0 BZ or Elaser M = ± 1 Thanks to Joe Brice

f + e v=1 J=3/2 v=0 J=3/2 f + e Zero-field

OH-CO Zeeman Spectroscopy Wavenumbers (cm-1) J. Chem. Phys. (2016), 145, 124310 Wavenumbers (cm-1)