Spectroscopy of CH 3 OH and ClOH in superfluid helium nanodroplets Paul Raston and Wolfgang Jäger Department of Chemistry, University of Alberta, Canada.

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Spectroscopy of CH 3 OH and ClOH in superfluid helium nanodroplets Paul Raston and Wolfgang Jäger Department of Chemistry, University of Alberta, Canada the OSU symposium,

diffusion pump 8000 L / s turbo pump 700 L / s turbo pump 700 L / s turbo pump 700 L / s turbo pump 340 L / s Cryostat, 28 K skimmer 500 μm doping cell quadrupole mass-spec nozzle 5 μm 2 Helium Nanodroplet Isolation (HENDI) spectrometer

diffusion pump 8000 L / s turbo pump 700 L / s turbo pump 700 L / s turbo pump 700 L / s turbo pump 340 L / s Cryostat, 28 K skimmer 500 μm doping cell quadrupole mass-spec nozzle 5 μm 3 Helium Nanodroplet Isolation (HENDI) spectrometer

diffusion pump 8000 L / s turbo pump 700 L / s turbo pump 700 L / s turbo pump 700 L / s turbo pump 340 L / s Cryostat, 28 K skimmer 500 μm doping cell microwave resonator quadrupole mass-spec nozzle 5 μm 4 Helium Nanodroplet Isolation (HENDI) spectrometer

Methanol: hindered internal rotor 5 A symmetry methanol has I(CH 3 )=3/2; E symmetry has I=1/2 g s is 8 for the A species and 4 for the E species C.C. Lin, J.D. Swalen, Rev. Mod. Phys., 31, 841 (1959) b c a

Methanol: Energy level diagram 6 b c a Expect that in going from T r = 300 K to ~0.4 K that the population distribution of will collapse into the J,K = 0,0 level for the A symmetry species, and the J,K = 1,-1 level for the E symmetry species. D. Bockelee-Morvan, J. Crovisier, P. Colom, D. Despois, Astron. Astrophys., 287, 647 (1994)

Methanol: Allowed rotational transitions from gs 7 Black arrows: observed transitions from several comets. D. Bockelee-Morvan, J. Crovisier, P. Colom, D. Despois, Astron. Astrophys., 287, 647 (1994) Pink arrows: Allowed a-type transitions from gs. Green arrows: Allowed b-type transitions from gs. b c a

Methanol depletion spectrum in superfluid helium Maximum signal corresponds to a 15% depletion of the droplet beam All are monomer peaks except lowest frequency one which is most likely dimer* 8 *

Methanol assignment; A species (J',K')-(J",K")free* (1,0)-(0,0) (1,1)-(0,0) I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) 9

Methanol assignment; A species I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Assume a- and b-type lines are slightly red shifted relative to gas phase 10 (J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,1)-(0,0)

Methanol assignment; A species I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Weak peaks either side of a-type R 1 (0) line look like P 1 (1) and R 1 (1) lines If they are, then R 0 (0) line should be at ~20 GHz This can be tested via IR-MW double resonance 11 (J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,1)-(0,0)

Laser tuned to cm-1 and microwave frequency scanned Decrease in depletion around GHz due to population transfer from J”=0 to J”=1 level 12 IR-MW double resonance υ OH =1 υ=0 J,K=0,0 1,0 2,0 1, cm -1

I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Microwaves tuned to GHz and laser frequency scanned Decrease in population of J”=0 level, and increase of J”=1 level 13 MW-IR double resonance (J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,1)-(0,0) (0,0)-(1,0) (2,0)-(1,0) υ OH =1 υ=0 1,0 2,0 1,1 J,K=0,0

(J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,1)-(0,0) (0,0)-(1,0) (2,0)-(1,0) I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Slight increase in depletion either side of b-type R 1 (0) line… 14 υ OH =1 υ=0 1,0 2,0 1,1 J,K=0,0 MW-IR double resonance

I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Slight increase in depletion either side of b-type R 1 (0) line… 15 MW-IR double resonance (J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,1)-(0,0) (0,0)-(1,0) (2,0)-(1,0) (1,1)-(1,0) (2,1)-(1,0) υ OH =1 υ=0 1,0 2,0 1,1 J,K=0,0

Back to the single resonance spectrum I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) A species methanol assigned; B(=C)=0.36 cm -1 ; D=0.007 cm (J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,1)-(0,0) (0,0)-(1,0) (2,0)-(1,0) (1,1)-(1,0) (2,1)-(1,0)

I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) A species methanol assigned; B(=C)=0.36 cm -1 ; D= cm -1 E species methanol should be straightforward if we assume B, and D same as for A species… 17 (J',K')-(J",K")free* (1,-1)-(1,-1) $ (2,-1)-(1,-1) $ (0,0)-(1,-1) (1,0)-(1,-1) (2,0)-(1,-1) (2,-2)-(1,-1) $ Methanol assignment; E species $ Perturbed lines

I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Only issue is that we are missing two peaks with K’=-1; they are thought to be broad and convoluted with other lines; predicted positions are shown in pink 18 (J',K')-(J",K")free*liquid He (1,-1)-(1,-1) $ ? (2,-1)-(1,-1) $ ? (0,0)-(1,-1) (1,0)-(1,-1) (2,0)-(1,-1) (2,-2)-(1,-1) $ Methanol assignment; E species

*E. Herbst, J.K. Messer, F.C. De Lucia, P. Helminger, J. Mol. Spectrosc., 108, 42 (1984) 19 Rovibrational analysis E = v 0 + B[J’(J’+1) - J”(J”+1)] - D J [(J’(J’+1)) 2 - (J”(J”+1)) 2 ] # I. Kleiner, G.T. Fraser, J.T. Hougen, A.S. Pine, J. Mol. Spectrosc., 147, 155 (1991) Most subband origins shifted by a fraction of a wavenumber, as expected constantgas phase*He dropletHe/gas from A species lines B D1.660E from E species lines B D1.660E subbandgas phase # He dropletgas-He A:K=0← A:K=1← E:K=0← E:K=-1← ? ?? E:K=-2←

ClOH effusive mass spectrum 20 Preparation: Cl 2 + H 2 O + HgO → HOCl + HgCl 2 + Cl 2 O +… H2OH2O N2N2 O2O2 CO 2 Cl 2 O HOCl

ClOH depletion spectrum in helium drops Peak at ~ cm -1 is CO 2 HOCl a-type lines around 3609 cm -1 ; b-type feature around 3629 cm -1 Inset shows optically selected mass spectra 21

ClOH depletion spectrum: a-type region Asymetric lineshapes suggests dynamical coupling of non superfluid helium to rotor* 22 *M.N. van Staveren, V.A. Apkarian, J. Chem. Phys., 133, (2010)

Summary of rotational constants M.Y. Choi, G.E. Douberly, T.M. Falconer, W.K. Lewis, C.M. Lindsay, J.M. Merritt, P.L. Stiles, R.E. Miller, Int. Rev. Phys. Chem., 25, 15 (2006) CH 3 OH (B) 23 B for CH 3 OH and ClOH are reduced to 43% of their gas phase values ClOH (A) ClOH (B)

Summary and outlook Found 10 lines for CH 3 OH which were assigned with the help of double resonance spectroscopy Could be interesting to investigate 13 CH 3 OH to see if missing E species (a-type) lines are present B constants of CH 3 OH and ClOH are reduced by ~60% in helium nanodroplets Need to do lineshape analysis for ClOH 24

Acknowledgements Jäger group (UA) Xu group (UA) Marie van Staveren and Prof. V.A. Apkarian (UCI) Funding: Natural Science and Engineering Research Council of Canada Canada Foundation for Innovation Alberta Science and Research Investments Program 25

CH 3 OH: CO stretch Moruzzi et al., Methanol spectral atlas vol. 1; 535 pages (1995) Did not scan over where the A symmetry methanol line should be! 26 (J',K')-(J",K")free*liquid HePrediction (1,0)-(0,0) ? (1,-1)-(1,-1) (2,-1)-(1,-1)

13 CH 3 OH: CO stretch (J',K')-(J",K")free*liquid He (1,0)-(0,0) (1,-1)-(1,-1) (2,-1)-(1,-1) I. Mukhopadhyay, R.M. Lees, W. Lewis-Bevan, J.W.C. Johns, J. Chem. Phys., 102, 6444 (1995) 27

MeOH_fine_M_sim_no_y0

CD 3 OH: OH stretch

HCCCN: SR

HCCCN: MW-IR DR