Professor

Contact Info

Office:
424 Chemistry Annex
Phone Number:
Lab Office:
476

Gary E. Douberly received a B.S. degree in chemistry from the University of Central Florida in 2000.  He received a Ph.D. in physical chemistry from the University of North Carolina at Chapel Hill in 2006 under the direction of Roger E. Miller and Tomas Baer. Following postdoctoral work with Michael A. Duncan at the University of Georgia, he began his faculty appointment at the University of Georgia in 2008. Professor Douberly has received the CAREER award from the National Science Foundation, the Early Career Award from the Department of Energy Office of Science, the Presidential Early Career Award for Scientists and Engineers (PECASE) from the White House Office of Science and Technology Policy, a JILA Visiting Fellowship, and the Journal of Physical Chemistry Lectureship Award. Most recently, Gary received the Coblentz Memorial Award from the Coblentz Society recognizing advancements in the field of Molecular Spectroscopy by a scientist under the age of 40.

Curriculum Vitae:
Other Affiliations:
Education:
  • B.S. University of Central Florida
  • Ph.D. University of North Carolina at Chapel Hill
Research Interests:

The Douberly research group has made significant contributions to the development of spectroscopic techniques designed for the helium nanodroplet isolation method.  They have employed this methodology to address a diverse set of fundamental problems in chemical physics.  The low temperature (0.4 K) and rapid cooling associated with helium droplets provides a perfectly suited medium to isolate and spectroscopically probe transient species, such as molecular radicals and carbenes.  Reactants sequentially added to helium droplets are often stabilized in high-energy, metastable configurations on the potential energy surface.  Single and double resonance infrared (IR) laser spectroscopic techniques are used to probe the structural and dynamical properties of these systems, often with sufficiently high resolution to resolve rotational fine structure. 

            Continuous, effusive pyrolysis sources of molecular radicals and carbenes have been optimized for doping helium nanodroplets, and several spectroscopic studies have been reported which describe the fundamental chemical physics of helium-solvated small radicals and carbenes. The methyl,1 ethyl,2 vinyl,3 propargyl,4 allyl5 and hydroxyl6 radicals have been probed, as have the hydroxycarbene7 and dihydroxycarbene8 systems.  These reports provided fundamental insights into the spectroscopy of these species and the interactions of these systems with the helium environment.  Rotational and vibrational state-dependent line broadening,1-3 dynamically-induced anomalous lambda doubling,6,9 and the solvent effect on tunneling dynamics3 are examples of the fundamental chemical physics that have been probed in these studies.  Moreover, recent Stark spectroscopy measurements of hydrogen bonded complexes involving the hydroxyl radical (OH-C2H2, OH-C2H4, and OH-H2O) have been interpreted via spectroscopic models developed by Douberly, which employ the spherical tensor operator formalism to account for the Stark effect in molecules possessing partially quenched electronic angular momentum.10,11 

            The Douberly group has leveraged the sequential pick-up technique developed by Scoles to investigate the mechanisms associated with several key elementary atmospheric and combustion reactions carried out inside low temperature helium droplets.  The rational for these studies is that spectroscopic measurements carried out downstream from the pick-up zones are capable of identifying the structural configuration of key intermediates along the reaction path, along with the associated product branching ratios.  The outcome of low temperature reactions involving hydrocarbon radicals and O2,4,5,12 or the hydroxyl radical (OH) and O2,13 have been probed with this methodology.  For example, a series of studies on the OH + O2 helium-mediated reaction revealed the barrierless formation of trans-HOOO,13-15 which was inconsistent with theoretical studies that had predicted a large entrance channel barrier above the reactant asymptote.  Higher level multireference configuration interaction computations of this system carried out by others confirmed the barrierless reaction path implied by Douberly’s experiments.  IR laser Stark spectroscopy of trans-HOOO revealed inertial components of the permanent electric dipole moment that were inconsistent with computations at the equilibrium geometry, consistent with a floppy species undergoing large-amplitude torsional motion.15  These experimental dipole components provided a stringent benchmark for theoretical computations of the ground state wavefunction, which eventually resulted in definitive computations of the dissociation energy and atmospheric abundance of this species.15

            Measurements have been reported in which dipeptides,16 ionic liquids17 or mixed acid-water clusters17,18 are assembled within helium droplets.  A two-stage oven source was developed which allowed for high-precision measurements of the gas-phase interconversion thermodynamics of the model di-peptide N-acetylglycine methylamide.16  Polarization spectroscopy of the ionic liquid 1Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide revealed a dipole moment of ~12 Debye, confirming definitively that these types of systems evaporate as intact ion-pairs.17  IR laser spectroscopy was used to probe the evolution of the spectral signatures associated with the formation and trapping of non-equilibrium (HCl)n-(H2O)m cluster geometries.18,19  This study was reported in collaboration with Andrey Vilesov and provided critical insights into controversial previous measurements of the onset of acid ionization in small acid-water clusters.  Most recently, a paper on the formation of exotic hydrogen-bonded water networks in helium droplets was published in the Journal of the American Chemical Society.20   The range of systems studied during Douberly’s independent career is both a testament to the versatility of the helium droplet method and the creativity of his research group.

 

  1. Morrison, A.M.; Raston, P.L.; Douberly, G.E., “Rotational relaxation dynamics of the methyl radical in helium nanodroplets” Journal of Physical Chemistry A, (2013), 117, 11640-11647. 
  2. Raston, P.L.; Agarwal, J.; Turney, J.M.; Schaefer, III H.F.; Douberly, G.E., “The Ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations” Journal of Chemical Physics, (2013), 138, 194303.
  3. Raston, P.L.; Liang, T.; Douberly, G.E., “Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He Nanodroplets” Journal of Chemical Physics, (2013), 138, 174302.
  4. Moradi, C.P.; Morrison, A.M.; Klippenstein, S.J.; Goldsmith, C.F.; Douberly, G.E., “The propargyl + O2 reaction in helium droplets: entrance channel barrier or not?” Journal of Physical Chemistry A, (2013), 117, 13626-13635.
  5. Leavitt, C.M.; Moradi, C.P.; Acrey, B.W.; Douberly, G.E., “Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals” Journal of Chemical Physics, (2013), 139, 234301.
  6. Raston, P.L.; Liang, T.; Douberly, G.E., “Anomalous L-doubling in the infrared spectrum of the hydroxyl radical in helium nanodroplets” Journal of Physical Chemistry A, (2013), 117, 8103-8110.
  7. Leavitt, C.M.; Moradi, C.P.; Stanton, J.F.; Douberly, G.E., “Communication: Helium Nanodroplet Isolation and Rovibrational Spectroscopy of Hydroxymethlyene” Journal of Chemical Physics, (2014), 140, 171102.
  8. Broderick, B.M.; McCaslin, L.; Moradi, C.P.; Stanton, J.F.; Douberly, G.E. “Reactive Intermediates in 4He Nanodroplets: Infrared Laser Stark Spectroscopy of Dihydroxycarbene” Journal of Chemical Physics, (2015), 142, 144309.
  9. Raston, P.L.; Liang, T.; Douberly, G.E., “Observation of the Q(3/2) L-doublet transitions for X 2P3/2 OD in Helium Nanodroplets” Molecular Physics, (2014), 112, 301-303.
  10. Moradi, C.P.; Douberly, G.E.; “On the Stark effect in open shell complexes exhibiting partially quenched electronic angular momentum: Infrared laser Stark spectroscopy of OH-C2H2, OH-C2H4, and OH-H2O” Journal of Molecular Spectroscopy, (2015), 314, 54-62.
  11. Hernandez, F.J.; Brice, J.T.; Leavitt, C.M.; Liang, T.; Raston, P.L.; Pino, G.A.; Douberly, G.E. "Mid-Infrared Signatures of Hydroxyl Containing Water Clusters: Infrared Laser Stark Spectroscopy of OH-H2O and OH(D2O)n (n=1-3)" Journal of Chemical Physics, (2015), 143, 164304.
  12. Morrison, A.M.; Agarwal, J.; Schaefer, III H.F.; Douberly, G.E., “Infrared laser spectroscopy of the CH3OO radical formed from the reaction of CH3 and O2 within a helium nanodroplet” Journal of Physical Chemistry A, (2012), 116, 5299-5304.
  13. Raston, P.L.; Liang, T.; Douberly, G.E., “Infrared spectroscopy of HOOO and DOOO in 4He nanodroplets” Journal of Chemical Physics, (2012), 137, 184302.
  14. Liang, T.; Raston, P.L.; Douberly, G.E., “Helium nanodroplet isolation spectroscopy and ab initio calculations of HO3-(O2)n clusters” ChemPhysChem, (2013), 14, 764-770.
  15. Liang, T.; Magers, D.B.; Raston, P.L.; Allen, W.D.; Douberly, G.E., “Dipole moment of the HOOO radical: Resolution of a structural enigma” Journal of Physical Chemistry Letters, (2013), 4, 3584-3589.
  16. Leavitt, C.M.; Moore, K.B.; Raston, P.L.; Agarwal, J.; Moody, G.H.; Shirley, C.C.; Schaefer, H.F.; Douberly, G.E. “Liquid Hot NAGMA Cooled to 0.4 Kelvin: Benchmark Thermochemistry of a Gas-Phase Peptide” Journal of Physical Chemistry A, (2014), 118, 9692-9700.
  17. Obi, E.I.; Leavitt, C.M.; Raston, P.L.; Moradi, C.P.; Flynn, S.D.; Vaghjiani, G.L.; Boatz, J.A.; Chambreau, S.D.; Douberly, G.E., “Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion- Pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide” Journal of Physical Chemistry A, (2013), 117, 9047-9056.
  18. Flynn, S.D.; Skvortsov D.; Morrison, A.M.; Liang,  T.; Choi,  M.Y.; Douberly, G.E.; Vilesov, A.F., “Infrared spectra of HCl-H2O clusters in helium nanodroplets” Journal of Physical Chemistry Letters, (2010), 1, 2233-2238.
  19. Morrison, A.M.; Flynn, S.D.; Liang, T.; Douberly, G.E., “Infrared spectroscopy of (HCl)m(H2O)n clusters in helium nanodroplets: Definitive assignments in the HCl stretch region” Journal of Physical Chemistry A, (2010), 114, 8090-8098.
  20. Douberly, G.E.; Miller, R.E.; Xantheas, S.S. “Formation of Exotic Networks of Water Clusters in Helium Droplets Facilitated by the Presence of Neon Atoms” Journal of the American Chemical Society, (2017), 139, 4152-4156.

 

Grants:

United States Air Force, Education Partnership Agreement, $443,500 “Infrared Optical Parametric Oscillator for Infrared-Infrared Double Resonance Experiments using Beams of Helium Nanodroplets,” 5/1/2018. (USAF EPA Number 18- -RW-01)

National Science Foundation, (CSDM-A), $436,406 “Helium Droplet Spectroscopy of Atmospherically Significant Reaction Intermediates” 5/1/17 to 4/30/20. (CHE-1664637)

Department of Energy, Office of Science, Basic Energy Sciences, Gas-Phase Chemical Physics Program (GPCP), $799,100 "Theoretical and Experimental Studies of Elementary Hydrocarbon Species and Their Reactions," 12/1/17 to 11/30/20. (DE-SC0018412)

Department of Energy, Office of Science, Early Career Research Program, $750,000 “Vibrational Spectroscopy of Transient Combustion Intermediates Trapped in Helium Nanodroplets” 7/1/12 to 06/30/17. (DE-FG02-12ER16298)

National Science Foundation, $618,505 “CAREER: Using Helium Nanodroplets to Probe the Structure and Thermochemistry of Biomolecular Building Blocks” 1/15/11 to 12/31/15. (CHE-1054742)

American Chemical Society Petroleum Research Fund, $100,000  "Vibrational Spectroscopy of Transient Combustion Intermediates Trapped in Helium Nanodroplets," 9/1/10 to 8/31/12.  (PRF No. 50223-DNI6)

Air Force Research Laboratory, Munitions Directorate (AFRL/RWME), $65,000  “Automation of an Optical Parametric Oscillator for the Characterization of Energetic Materials Synthesized in Helium Nanodroplets,” 8/1/10 to 7/31/11. (FA8651-10-C-0272)

University of Georgia Research Foundation, $8,925  "Vibrational Spectroscopy of Transient Combustion Intermediates Trapped in Helium Nanodroplets," 1/1/10 to 12/31/10. (1164)

Selected Publications:

 

39.  Franke, P.R.; Douberly, G.E. “The Rotamers of Isoprene: Infrared Spectroscopy in Helium Droplets and Ab Initio Thermochemistry” Journal of Physical Chemistry A, (2018), 122, 148-158.  10.1021/acs.jpca.7b10260 

38.  Brice, J.T.; Franke, P.R.; Douberly, G.E. “Sequential Capture of O(3P) and HCN by Helium Nanodroplets: Infrared Spectroscopy and Ab Initio Computations of the O-HCN Complex” Journal of Physical Chemistry A, (2017), 121, 9466-9473. PDF       

37.  Brown, A.R; Franke, P.R.; Douberly, G.E. “Helium Nanodroplet Isolation of the Cyclobutyl, 1-Methylallyl and Allylcarbinyl Radicals: Infrared Spectroscopy and Ab Initio Computations” Journal of Physical Chemistry A, (2017), 121, 7576-7587. PDF

36.  Raston, P.L; Obi, E.I.; Douberly, G.E. “Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets” Journal of Physical Chemistry A, (2017), 121, 7597-7602. PDF

35.  Straatsma C.J.E.; Fabrikant, M.I.; Douberly, G.E.; Lewandowski, H.J. “Production of Carbon Clusters Cto C12 with a Cryogenic Buffer-Gas Beam Source” Journal of Chemical Physics, (2017), 147, 124201. PDF

34.  Douberly, G.E.; Miller, R.E.; Xantheas, S.S. “Formation of Exotic Networks of Water Clusters in Helium Droplets Facilitated by the Presence of Neon Atoms” Journal of the American Chemical Society, (2017), 139, 4152-4156. PDF

33.  Franke, P.R.; Tabor, D.; Moradi, C.P.; Douberly, G.E.; Agarwal, J.; Schaefer, H.F.; Sibert, E.L. “Infrared Laser Spectroscopy of the n-propyl and i-propyl Radicals: Stretch-Bend Fermi Coupling in the Alkyl CH Stretch Region” Journal of Chemical Physics, (2016), 145, 224304. PDF

32.  Brice, J.T.; Liang, T.; Raston, P.L.; McCoy, A.B.; Douberly, G.E. “Infrared Stark and Zeeman spectroscopy of OH-CO: The entrance channel complex along the OH + CO →  trans-HOCO reaction pathway” Journal of Chemical Physics, (2016), 145, 124310. PDF

31.  Kaufmann, M.; Leicht, D.; Havenith, M.; Broderick, B.M.; Douberly, G.E. “Infrared Spectroscopy of the Tropyl Radical in Helium Droplets” Journal of Physical Chemistry A, (2016), 120, 6768-6773. PDF

30.  Moradi, C.P.; Xie, C.; Kaufmann, M.; Guo, H.; Douberly, G.E.  "Two-center three-electron bonding in ClNH3 revealed via helium droplet infrared laser Stark spectroscopy: Entrance channel complex along the Cl + NH3 → ClNH2 + H reaction" Journal of Chemical Physics, (2016), 144, 164301. PDF

29.  Federico J. Hernandez, Joseph T. Brice, Christopher M. Leavitt, Tao Liang, Paul L. Raston, Gustavo A. Pino, and Gary E. Douberly "Mid-Infrared Signatures of Hydroxyl Containing Water Clusters: Infrared Laser Stark Spectroscopy of OH-H2O and OH(D2O)n (n=1-3)" Journal of Chemical Physics, (2015), 143, 164304. PDF

28. Bernadette M. Broderick, Christopher P. Moradi, and Gary E. Douberly "Infrared Laser Stark Spectroscopy of Hydroxymethoxycarbene in 4He Nanodroplets" Chemical Physics Letters, (2015), 639, 99-104. PDF

27.  Federico J. Hernandez, Joseph T. Brice, Christopher M. Leavitt, Gustavo A. Pino, and Gary E. Douberly "Infrared Spectroscopy of OH-CH3OH: Hydrogen-Bonded Intermediate Along the Hydrogen Abstraction Reaction Path" Journal of Physical Chemistry A, (2015), 119, 8125–8132.  PDF

26.  Christopher P. Moradi and Gary E. Douberly “Infrared Laser Spectroscopy of the L-shaped Cl-HCl Complex Formed in Superfluid 4He Nanodroplets” Journal of Physical Chemistry A, (2015), 119, 12028-12035. 

25.  Christopher P. Moradi and Gary E. Douberly “On the Stark Effect in Open Shell Complexes Exhibiting Partially Quenched Electronic Angular Momentum: Infrared Laser Stark Spectroscopy of OH-C2H2, OH-C2H4, and OH-H2O” Journal of Molecular Spectroscopy, (2015), 314, 54-62. PDF

24.  Bernadette M. Broderick, Laura McCaslin, Christopher P. Moradi, John F. Stanton and Gary E. Douberly “Reactive Intermediates in 4He Nanodroplets: Infrared Laser Stark Spectroscopy of Dihydroxycarbene” Journal of Chemical Physics, (2015), 142, 144309.  PDF

23.  Gary E. Douberly, Paul L. Raston, Tao Liang and Mark D. Marshall, “Infrared Rovibrational Spectroscopy of OH–C2H2 in 4He nanodroplets: Parity Splitting due to Partially Quenched Electronic Angular Momentum” Journal of Chemical Physics, (2015), 142, 134306.  PDF

22.  Leavitt, C.M.; Moore, K.B.; Raston, P.L.; Agarwal, J.; Moody, G.H.; Shirley, C.C.; Schaefer, H.F.; Douberly, G.E. “Liquid Hot NAGMA Cooled to 0.4 Kelvin: Benchmark Thermochemistry of a Gas-Phase Peptide” Journal of Physical Chemistry A, (2014), 118, 9692-9700.  PDF

21. Raston, P.L.; Douberly, G.E.; Jäger W. “Single and Double Resonance Spectroscopy of Methanol Embedded in Superfluid Helium Nanodroplets” Journal of Chemical Physics, (2014), 141, 044301.  PDF

20. Leavitt, C.M.; Moradi, C.P.; Stanton, J.F.; Douberly, G.E., “Communication: Helium Nanodroplet Isolation and Rovibrational Spectroscopy of Hydroxymethlyene” Journal of Chemical Physics, (2014), 140, 171102.  PDF

19. Raston, P.L.; Liang, T.; Douberly, G.E., “Observation of the Q(3/2) Λ-doublet transitions for X2Π3/2OD in Helium Nanodroplets” Molecular Physics, (2014), 112, 301-303.  PDF

18. Leavitt, C.M.; Moradi, C.P.; Acrey, B.W.; Douberly, G.E., “Infrared laser spectroscopy of the helium-solvated allyl and allyl peroxy radicals” Journal of Chemical Physics, (2013), 139, 234301.  PDF

17. Liang, T.; Magers, D.B.; Raston, P.L.; Allen, W.D.; Douberly, G.E., “Dipole moment of the HOOO radical: Resolution of a structural enigma” Journal of Physical Chemistry Letters, (2013), 4, 3584-3589.  PDF

16. Raston, P.L.; Douberly, G.E., “Rovibrational spectroscopy of formaldehyde in helium nanodroplets” Journal of Molecular Spectroscopy, (2013), 292, 15-19.  PDF

15. Gomez, L.F.; Sliter, R.; Skvortsov, D.; Hoshina, H.; Douberly, G.E.; Vilesov, A.F., “Infrared spectra in the 3 um region of ethane and ethane clusters in He droplets” Journal of Physical Chemistry A, (2013), 117, 13648-13653.  PDF

14. Moradi, C.P.; Morrison, A.M.; Klippenstein, S.J.; Goldsmith, C.F.; Douberly, G.E., “The propargyl + O2reaction in helium droplets: entrance channel barrier or not?” Journal of Physical Chemistry A, (2013), 117, 13626-13635.  PDF

13. Obi, E.I.; Leavitt, C.M.; Raston, P.L.; Moradi, C.P.; Flynn, S.D.; Vaghjiani, G.L.; Boatz, J.A.; Chambreau, S.D.; Douberly, G.E., “Helium Nanodroplet Isolation and Infrared Spectroscopy of the Isolated Ion- Pair 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide” Journal of Physical Chemistry A, (2013), 117, 9047-9056.  PDF

12. Raston, P.L.; Agarwal, J.; Turney, J.M.; Schaefer, III H.F.; Douberly, G.E., “The Ethyl radical in superfluid helium nanodroplets: Rovibrational spectroscopy and ab initio computations” Journal of Chemical Physics, (2013), 138, 194303.  PDF

11. Raston, P.L.; Liang, T.; Douberly, G.E., “Infrared spectroscopy and tunneling dynamics of the vinyl radical in 4He Nanodroplets” Journal of Chemical Physics, (2013), 138, 174302.  PDF

10. Raston, P.L.; Liang, T.; Douberly, G.E., “Anomalous Λ-doubling in the infrared spectrum of the hydroxyl radical in helium nanodroplets” Journal of Physical Chemistry A, (2013), 117, 8103-8110.  PDF

 9.  Morrison, A.M.; Liang, T.; Douberly, G.E., “Automation of an ‘Aculight’ continuous-wave Optical Parametric Oscillator” Review of Scientific Instruments, (2013), 84, 013102.  PDF      

 8.  Liang, T.; Raston, P.L.; Douberly, G.E., “Helium nanodroplet isolation spectroscopy and ab initio calculations of HO3-(O2)n clusters” ChemPhysChem, (2013), 14, 764-770.  PDF

 7.  Morrison, A.M.; Raston, P.L.; Douberly, G.E., “Rotational relaxation dynamics of the methyl radical in helium nanodroplets” Journal of Physical Chemistry A, (2013), 117, 11640-11647.  PDF

 6.  Raston, P.L.; Liang, T.; Douberly, G.E., “Infrared spectroscopy of HOOO and DOOO in 4He nanodroplets” Journal of Chemical Physics, (2012), 137, 184302.  PDF

 5.  Liang, T.; Douberly, G.E., “On the Al + HCN reaction in helium nanodroplets” Chemical Physics Letters, (2012), 551, 54-59.  PDF

 4.  Morrison, A.M.; Agarwal, J.; Schaefer, III H.F.; Douberly, G.E., “Infrared laser spectroscopy of the CH3OO radical formed from the reaction of CH3 and O2 within a helium nanodroplet” Journal of Physical Chemistry A, (2012), 116, 5299-5304.  PDF

 3.  Liang, T.; Flynn, S.D.; Morrison, A.M.; Douberly, G.E., “Quantum cascade laser spectroscopy and photo-induced chemistry of Al-(CO)n clusters in helium nanodroplets” Journal of Physical Chemistry A, (2011), 115, 7437-7447.  PDF

 2.  Morrison, A.M.; Flynn, S.D.; Liang, T.; Douberly, G.E., “Infrared spectroscopy of (HCl)m(H2O)n clusters in helium nanodroplets: Definitive assignments in the HCl stretch region” Journal of Physical Chemistry A, (2010), 114, 8090-8098.  PDF

 1.  Flynn, S.D.; Skvortsov D.; Morrison, A.M.; Liang,  T.; Choi,  M.Y.; Douberly, G.E.; Vilesov, A.F., “Infrared spectra of HCl-H2O clusters in helium nanodroplets” Journal of Physical Chemistry Letters, (2010), 1, 2233-2238.  PDF