Institut fr Physikalische Chemie Elektrochemie Lehrgebiet A ROTATIONAL

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A 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 Zentrum für Festkörperchemie & Neue Materialien Trevor J Sears Brookhaven National Laboratory, Upton, NY N. E. Shafer-Ray University of Oklahoma, Norman, OK Columbus, OH, June Columbus, June 20132006

Rotational Spectroscopy in the Time-Domain: Technique, Capabilities & Directions Advantages of FT-microwave spectroscopy Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A high resolution & sensitivity: Resonator & Jet: COBRA instrument Sample preparation for FT-MW Experiment non-volatile species: LASER-Ablation Source: CATS technique Precise FTMW Characterization electronic angular momentum species: in-situ generation: Pb. F, Yb. F, etc. - Stark effect - Zeeman effect Zentrum für Festkörperchemie & Neue Materialien Future High Precision FTMW Investigation e-EDM sensitive species: Polarization direction: DREAM-FTMW machine Columbus, OH, June Columbus, June 20132006

Coaxial oriented Beam-Resonator Arrangement (COBRA): molecular excitation Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A many two-level systems before excitation pulse: Eb Ea dipole moments cancel 1μs t MW pulse single particle, Schrödinger equation: wavefunction density matrix ensemble properties, von Neumann equation density matrix: Zentrum für Festkörperchemie & Neue Materialien J. -U. Grabow, W. Stahl, Z. Naturforsch. 45 a, 1043 (1990). population: (no) coherence: Columbus, OH, June Columbus, June 20132006

Coaxial oriented Beam-Resonator Arrangement (COBRA): molecular response Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A after excitation pulse: oscillating macroscopic dipole moment E T = 100μs MW signal t density matrix: population: coherence: Time Domain, FID Zentrum für Festkörperchemie & Neue Materialien U. Andresen, H. Dreizler, J. -U. Grabow, W. Stahl, Rev. Sci. Instrum. 61, 3694 (1990). Fourier Transform Frequency Domain, Spectrum Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A COBRA chamber Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Fabry-Pérot Type Resonator: Spherical Reflectors Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Spherical Reflector: Transmit & Receive Antennae Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A high-frequency antennae supersonic-jet source low-frequency antennae Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Te. Se: Electronic Data From Pure Rotational Spectra 125 Te 77 Se J‘ ← J 4← 3 req = 235. 904038(71) pm Resolution: 0. 0000001 cm-1 Deike Banser, Melanie Schnell, Jens-Uwe Grabow, Emilio J. Cocinero, Alberto Lesarri, and Jose L. Alonso, Angew. Chem. Int. Ed. 2005, 44, 6311. Accuracy: 0. 00000001 cm-1 Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

MSe Multi-Isotopolog Potential Fits: Tracking down tiny effects of different origin Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A , , Born-Oppenheimer breakdown correction coefficients: electronic state Zentrum für Festkörperchemie & L. Neue Materialien nuclear volume Bizzocchi, B. M. Giuliano, M. Hess, J. -U. Grabow, J. Chem. Phys. 126, 114305(2007). B. M. Giuliano, L. Bizzocchi, S. Cooke, D. Banser, M. Hess, J. Fritzsche, J. -U. Grabow, PCCP 10, 2078(2008). Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A What Would An electron Electric Dipole Moment (e-EDM) Do? 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. To search for an e-EDM look for DU=U+M –U-M in a strong (internal) E field at alternately parallel/anti-parallel B-fields. Zentrum für Festkörperchemie & Neue Materialien Major Difficulty: A background magnetic field mimics an electron EDM. A polar heavy atom diatomic in an electric field parallel or anti-parallel to an magnetic field: • with a zero e−EDM the energy between states that differ only by MF is independent of the relative direction. • a nonzero e−EDM would cause a small difference in this energy for the parallel and anti-parallel configuration. Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Molecules with electronic angular momentum: Heavy-metal fluorides F Zentrum für Festkörperchemie & Neue Materialien Pb un-paired p electron: 2 P 1/2 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 measurements @ reasonabe B-field control w linear Stark-effect (Eint~30 GV/cm) at moderate ext. fields Columbus, June 2013

Generation of Pb. F seeded supersonic jet: Coaxial Ablation Twin Source (CATS) Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A rotating/translating rods: Nd: YAG LASER I elements, alloys, compounds bulk material, compressed powder supersonic expansion SF 6(1%) / Ne @ ~500 k. Pa Nd: YAG LASER II Zentrum für Festkörperchemie & Neue Materialien elementary Pb Columbus, OH, June Columbus, June 20132006

Molecules with electronic angular momentum: Zeeman-effect of 208 Pb. F Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Splitting/MHz J, F = 1/2, 1 → 3/2, 1 0. 2 0. 15 J, F = 1/2, 0 → 3/2, 1 0. 1 Parallel Magnetic Field: ∆M = 0 0. 05 Parallel Magnetic Field Perpendicular Magnetic Field 0 -1 -0. 5 0 0. 5 B / gauss 1 -0. 05 -0. 1 Perpendicular Magnetic Field: ∆M = ± 1 -0. 15 Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Molecules with electronic angular momentum /w nuclear hfs: Concept for a molecular spectroscopy e-EDM experiment Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A 208 Pb 19 F 207 Pb 19 F 3 -spin system: e-, F, Pb 2 -spin system: e-, F Zentrum für Festkörperchemie & Neue Materialien accidentally close-lying 207 Pb 19 F states of opposite parity: complete polarizability (yielding ~30 GV/cm effective internal fields) at moderate laboratory E fields (200 V/cm) Columbus, OH, June Columbus, June 20132006

Molecules with electronic angular momentum w/o nuclear hfs: Concept for a molecular spectroscopy e-EDM experiment Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A E=0 E≠ 0 J=2 from A. Leanhardt WC: 3Δ electronic ground state 1 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). J=1 Current limit (de =10. 5 x 10 -28 e cm-1): Zentrum für Festkörperchemie & Neue Materialien would lead to e-EDM effect of 50 m. Hz Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Where are we now? alternative interpretation of dci: A i = -di + dci J(J+1) centrifugal correction to A i accuracy reached with: - standard COBRA-FTMW instrument - <5 d after Pb rod was first inserted Zentrum für Festkörperchemie & Neue Materialien measurement linewidth comparable to that in study of Yb. F: J. Hudson, B. Sauer, M. Tarbutt, E. Hinds, Phys. Rev. Lett. 89 (2002) 23003. Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Origin Of dc 1 And dc 2 ? Comparison to high level ab-initio calculations in preparation FS-RCCSD method large basis sets Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Where are we now? nuclear anapole moment Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Pb. F: P-odd, T-odd effects nuclear anapole moment constants V. V. Flambaum, I. B. Khriplovich, O. P. Sushkov, Phys. Lett. B 146 (1984) 367. Zentrum für Festkörperchemie & Neue Materialien e-EDM Current limit (from Tl atomic spectroscopy): de =10. 5 x 10 -28 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: WP, T κP, T+ Wd de = 17 m. Hz Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A P-odd – Interaction Constant Wp: ab-initio calculations Zentrum für Festkörperchemie & Neue Materialien A. Borschevsky, M. Ilias, V. A. Dzuba, K. Beloy, V. V. Flambaum, P. Schwerdtfeger, Phys. Rev. A 85, 052509 (2012 Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Molecules with electronic angular momentum: Ytterbium Fluoride F Zentrum für Festkörperchemie & Neue Materialien Yb un-paired s electron: 2 S 1/2 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 measurements @ precise B-field control s electron penetrates nucleus: nuclear anapole moment sensitivity Columbus, June 2013

Generation of WC seeded supersonic jet: Coaxial Ablation Twin Source (CATS) Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A rotating/translating rods: Nd: YAG LASER I elements, alloys, compounds bulk material, compressed powder supersonic expansion SF 6(1%) / Ne @ ~500 k. Pa or pure Ne @ ~500 k. Pa Nd: YAG LASER II Zentrum für Festkörperchemie & Neue Materialien elementary Yb or Yb. F Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A COBRA-FTMW Yb. F Measurements Measured 12 new and 4 previous* Yb. F lines: 174 Yb. F • 1 170 Yb. F lines • 4 171 Yb. F lines# • 4 172 Yb. F lines • 4 174 Yb. F lines • 3 176 Yb. F lines # Spin ½ Yb nucleus Zentrum für Festkörperchemie & Neue Materialien *C. S. Dickinson, S. A. Coxon, N. R. Walker, M. C. L. Gerry , J. Chem. Phys. 115, 6979 (2001). Columbus, OH, June Columbus, June 20132006

Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Yb. F multi-isotopologue fit#+ results 174 Yb 19 F V=0 Y 01 7256. 444(80) / MHz V=1 -0. 145(80) Y 11 / MHz -44. 9378(152) Y 02 / MHz -0. 007159* / MHz D / MHz -13. 418163(310) 0. 00397552(309) -0. 006904* -33. 80950( 49) 0. 0043202( 37) b. F(F) / MHz 170. 26361( 68) 168. 8030(110) c(F) / MHz 85. 4035( 32) 86. 7127(134) c. D(F) / MHz 0. 001552( 70) 0. 00216( 38) CI(F) / MHz 0. 014544(177) 0. 01548( 66) * fixed to value taken from: K. L. Dunfield, C. Linton, T. E. Clarke, J. Mc. Bride, A. G. Adam, J. R. D. Peers, J. Mol. Spectrosc. 174, 433 (1995). Zentrum für Festkörperchemie & Neue Materialien # 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). + including RF transitions taken from: B. E. Sauer, J. Wang, and E. A. Hinds, J. Chem. Phys. 105, 7412 (1996). Columbus, OH, June Columbus, June 20132006

Diatomic Rotation - The quest for the e-EDM accelarated by Molecular Spectroscopy: Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A DREAM - FTMW Zentrum für Festkörperchemie & Neue Materialien Columbus, OH, June Columbus, June 20132006

Acknowledgement Institut für Physikalische Chemie & Elektrochemie, Lehrgebiet A Deutsche Forschungsgemeinschaft (DFG) Deutscher Akademischer Austauschdienst (DAAD) Fonds der Chemischen Industrie (FCI) Land Niedersachsen Aaron Leanhardt, U. Michigan Zentrum für Festkörperchemie & Neue Materialien Feinmechanikwerkstatt des Instituts für Physikalische Chemie W. Rogge Columbus, OH, June Columbus, June 20132006