Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 ROTATIONAL SPECTRA IN SERVICE OF PARTICLE PHYSICS - ZEEMAN & HYPERFINE EFFECTS Jens-Uwe Grabow, Lukas D. Alphei Gottfried-Wilhelm-Leibniz-Universität Hannover Richard J Mawhorter, Alexander Baum, Zachary Glassmann, Benjamin Girodas Pomona College, Claremont, CA Trevor J Sears Brookhaven National Laboratory, Upton, NY N.E. Shafer-Ray University of Oklahoma, Norman, OK

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Advantages of FT-microwave spectroscopy Sample preparation for FT-MW Experiment Precise FTMW Characterization Future High Precision FTMW Investigation Rotational Spectroscopy in the Time-Domain: Technique, Capabilities & Directions non-volatile species: LASER-Ablation Source: CATS technique non-volatile species: LASER-Ablation Source: CATS technique high resolution & sensitivity: Resonator & Jet: COBRA instrument electronic angular momentum species: in-situ generation: PbF, YbF, etc. - Stark effect - Zeeman effect e-EDM sensitive species: Polarization direction: DREAM-FTMW machine

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Coaxial oriented Beam-Resonator Arrangement (COBRA): molecular excitation t MW pulse 1μs before excitation pulse: dipole moments cancel EbEb EaEa many two-level systems single particle, Schrödinger equation: ensemble properties, von Neumann equation wavefunction density matrix density matrix: (no) coherence: population: J.-U. Grabow, W. Stahl, Z. Naturforsch. 45a, 1043 (1990).

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Coaxial oriented Beam-Resonator Arrangement (COBRA): molecular response E t T = 100μs MW signal after excitation pulse:oscillating macroscopic dipole moment density matrix: coherence: population: Fourier Transform Frequency Domain, Spectrum Time Domain, FID U. Andresen, H. Dreizler, J.-U. Grabow, W. Stahl, Rev.Sci.Instrum. 61, 3694 (1990). J.-U. Grabow, W. Stahl, H. Dreizler, Rev.Sci.Instrum. 67, 4072 (1996).

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 COBRA chamber

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Fabry-Pérot Type Resonator: Spherical Reflectors

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Spherical Reflector: Transmit & Receive Antennae supersonic-jet source high-frequency antennae low-frequency antennae

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 TeSe: Electronic Data From Pure Rotational Spectra 125 Te 77 Se J 4 3 Resolution: cm -1 Accuracy: cm -1 r eq = (71) pm Deike Banser, Melanie Schnell, Jens-Uwe Grabow, Emilio J. Cocinero, Alberto Lesarri, and Jose L. Alonso, Angew. Chem. Int. Ed. 2005, 44, 6311.

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 MSe Multi-Isotopolog Potential Fits: Tracking down tiny effects of different origin,, L. Bizzocchi, B.M. Giuliano, M. Hess, J.-U. Grabow, J. Chem. Phys. 126, (2007). B.M. Giuliano, L. Bizzocchi, S. Cooke, D. Banser, M. Hess, J. Fritzsche, J.-U. Grabow, PCCP 10, 2078(2008). Born-Oppenheimer breakdown correction coefficients: electronic state nuclear volume

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Symmetry leads to ±M-degeneracy of any molecule/atom that is not broken by an E-field along quantization axis. The existence of an electron electric dipole moment would break this symmetry. Major Difficulty: A background magnetic field mimics an electron EDM. What Would An electron Electric Dipole Moment (e-EDM) Do? To search for an e-EDM look for U =U +M –U -M in a strong (internal) E field at alternately parallel/anti-parallel B-fields. A polar heavy atom diatomic in an electric field parallel or anti-parallel to an magnetic field: with a zero eEDM the energy between states that differ only by M F is independent of the relative direction. a nonzero eEDM would cause a small difference in this energy for the parallel and anti-parallel configuration.

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Molecules with electronic angular momentum: Heavy-metal fluorides Pb F un-paired p electron: 2 ground state small g-factor hfs due to F (and 207 Pb) spin I = 1/2 large polarizability heavy Pb nucleus: relativistic effects candidate for e-EDM reasonabe B-field control \w linear Stark-effect (E int ~30 GV/cm) at moderate ext. fields

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Generation of PbF seeded supersonic jet: Coaxial Ablation Twin Source (CATS) SF 6 (1%) / ~500 kPa Nd:YAG LASER I Nd:YAG LASER II supersonic expansion rotating/translating rods:elements, alloys, compounds bulk material, compressed powder elementary Pb

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Molecules with electronic angular momentum: Zeeman-effect of 208 PbF Splitting/MHz B / gauss Perpendicular Magnetic Field: M = ± 1 Parallel Magnetic Field: M = 0 J, F = 1/2, 0 3/2, 1 J, F = 1/2, 1 3/2, 1

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Molecules with electronic angular momentum /w nuclear hfs: Concept for a molecular spectroscopy e-EDM experiment accidentally close-lying 207 Pb 19 F states of opposite parity: complete polarizability (yielding ~30GV/cm effective internal fields) at moderate laboratory E fields (200V/cm) 2-spin system: e-, F 3-spin system: e-, F, Pb 208 Pb 19 F 207 Pb 19 F

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Molecules with electronic angular momentum w/o nuclear hfs: Concept for a molecular spectroscopy e-EDM experiment WC: 3 Δ 1 electronic ground state small g-factor Systematically very close-lying Λ-doublets of opposite parity: fields of E ~ 1 V/cm are sufficient for complete polarization (60 GV/cm). from A. Leanhardt Current limit (d e =10.5 x e cm -1 ): would lead to e-EDM effect of 50 mHz E = 0E 0 J = 2 J = 1

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Where are we now? accuracy reached with: - standard COBRA-FTMW instrument - <5 d after Pb rod was first inserted measurement linewidth comparable to that in study of YbF: J. Hudson, B. Sauer, M. Tarbutt, E. Hinds, Phys. Rev. Lett. 89 (2002) A i = -d i + d ci J(J+1) alternative interpretation of d ci : centrifugal correction to A i

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Origin Of d c1 And d c2 ? Comparison to high level ab-initio calculations in preparation FS-RCCSD method large basis sets

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Where are we now? nuclear anapole moment

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 PbF: P-odd, T-odd effects Current limit (from Tl atomic spectroscopy): d e =10.5 x e cm -1 J. J. Hudson, D. M. Kara, I. J. Smallman, B. E. Sauer, M. A. Tarbutt, E. A. Hinds, Nature 473 (2011) 493 corresponds to: W P,T κ P,T + W d d e = 17 mHz nuclear anapole moment constants e-EDM V. V. Flambaum, I. B. Khriplovich, O. P. Sushkov, Phys. Lett. B 146 (1984) 367.

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 P-odd – Interaction Constant W p : ab-initio calculations A. Borschevsky, M. Ilias, V. A. Dzuba, K. Beloy, V. V. Flambaum, P. Schwerdtfeger, Phys. Rev. A 85, (2012)

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Molecules with electronic angular momentum: Ytterbium Fluoride Yb F un-paired s electron: 2 ground state small g-factor hfs due to F spin I = ½ ( 171/173 Yb: 1/2,5/2) large polarizability heavy Yb nucleus: relativistic effects candidate for e-EDM precise B-field control s electron penetrates nucleus: nuclear anapole moment sensitivity

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Generation of WC seeded supersonic jet: Coaxial Ablation Twin Source (CATS) SF 6 (1%) / ~500 kPa or pure ~500 kPa Nd:YAG LASER I Nd:YAG LASER II supersonic expansion rotating/translating rods:elements, alloys, compounds bulk material, compressed powder elementary Yb or YbF

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 COBRA-FTMW YbF Measurements Measured 12 new and 4 previous* YbF lines: 1 170YbF lines 4 171YbF lines# 4 172YbF lines 4 174YbF lines 3 176YbF lines # Spin ½ Yb nucleus 174 YbF *C.S. Dickinson, S.A. Coxon, N.R. Walker, M.C.L. Gerry, J. Chem. Phys. 115, 6979 (2001).

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 YbF multi-isotopologue fit #+ results 174 Yb 19 FV=0V=1 Y 01 / MHz (80) (80) Y 11 / MHz (152) Y 02 / MHz * * / MHz (310) ( 49) D / MHz (309) ( 37) b F (F) / MHz ( 68) (110) c(F) / MHz ( 32) (134) c D (F) / MHz ( 70) ( 38) C I (F) / MHz (177) ( 66) * fixed to value taken from: K.L. Dunfield, C. Linton, T.E. Clarke, J. McBride, A.G. Adam, J.R.D. Peers, J. Mol. Spectrosc. 174, 433 (1995). + including RF transitions taken from: B. E. Sauer, J. Wang, and E. A. Hinds, J. Chem. Phys. 105, 7412 (1996). # including v=1 transitions taken from: C.S. Dickinson, S.A. Coxon, N.R. Walker, M.C.L. Gerry, J. Chem. Phys. 115, 6979 (2001).

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Diatomic Rotation - The quest for the e-EDM accelarated by Molecular Spectroscopy: DREAM - FTMW

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Columbus, OH, June 2006.ppt Zentrum für Festkörperchemie & Neue Materialien Columbus, June 2013 Acknowledgement Aaron Leanhardt, U. Michigan Feinmechanikwerkstatt des Instituts für Physikalische Chemie W. Rogge Deutsche Forschungsgemeinschaft (DFG) Deutscher Akademischer Austauschdienst (DAAD) Fonds der Chemischen Industrie (FCI) Land Niedersachsen