Alexander Yakushev GSI Helmholtzzentrum für Schwerionenforschung GmbH Gas phase chemistry of the SHE Results Instrumentations Perspectives FUSHE Workshop 2012, , Weilrod GERMANY

Outline  Introduction  Short history and goals of SHE chemistry  Last achievements: - studies of Cn and E114 by thermochromatography - attempts to study of E113 - re-measure of DbBr 5 - “new” organometallic compounds  Instrumentations: - separation devices - detectors - pre-separation  Further developments for future experiments: - sensitivity - background suppression - faster chemistry – vacuum chromatography - new volatile compounds and new column surfaces  Conclusion FUSHE Workshop 2012, , Weilrod GERMANY

N Z Fast Chemistry Element   + EC SF -- New Compounds Elements FUSHE Workshop 2012, , Weilrod GERMANY Introduction: Regions of interest (i)

1H1H 2 He 3 Li 4 Be 5B5B 6C6C 7N7N 8O8O 9F9F 10 Ne 11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar 19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn 31 Ga 32 Ge 33 As 34 Se 35 Br 36 Kr 37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe 55 Cs 56 Ba 57 La* 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 78 Pt 79 Au 80 Hg 81 Tl 82 Pb 83 Bi 84 Po 85 At 86 Rn 87 Fr 88 Ra 89 Ac* * 104 Rf 105 Db 106 Sg 107 Bh 108 Hs 109 Mt 110 Ds 111 Rg 112 Cn 113 Uut 114 Uuq 115 Uup 116 Uuh 117 Uus 118 Uuo 58 Ce 59 Pr 60 Nd 61 Pm 62 Sm 63 Eu 64 Gd 65 Tb 66 Dy 67 Ho 68 Er 69 Tm 70 Yb 71 Lu 90 Th 91 Pa 92 U 93 Np 94 Pu 95 Am 96 Cm 97 Bk 98 Cf 99 Es 100 Fm 101 Md 102 No 103 Lr *Lanthanoides **Actinoides transactinides = superheavy elements (SHE) s2s2 s2d1s2d1 s 2 d 10 p - elements d - elements Introduction: Regions of interest (ii)

Production of nucleus  Beam  Target  Recoil chamber …. Separation and transport  Gas or aerosol jet  Chemical yield  Chemical kinetics …. Detection of decay  Transport to a detector  Sample  Detection efficiency and resolution …. Introduction: Chemistry with single atoms (i) FUSHE Workshop 2012, , Weilrod GERMANY

SHE chemistry challenges: - highest chemical yield  fast and „easy“ - effective transport of SHE atoms from a target area to a setup for the chemical separation - separation from a carrier (if needed) - effectiove chemical separation in one step from unwanted products - transport to a detection device and measurement Introduction: Chemistry with single atoms (ii) FUSHE Workshop 2012, , Weilrod GERMANY

1H1H 2 He 3 Li 4 Be 5B5B 6C6C 7N7N 8O8O 9F9F 10 Ne 11 Na 12 Mg 13 Al 14 Si 15 P 16 S 17 Cl 18 Ar 19 K 20 Ca 21 Sc 22 Ti 23 V 24 Cr 25 Mn 26 Fe 27 Co 28 Ni 29 Cu 30 Zn 31 Ga 32 Ge 33 As 34 Se 35 Br 36 Kr 37 Rb 38 Sr 39 Y 40 Zr 41 Nb 42 Mo 43 Tc 44 Ru 45 Rh 46 Pd 47 Ag 48 Cd 49 In 50 Sn 51 Sb 52 Te 53 I 54 Xe 55 Cs 56 Ba 57 La* 72 Hf 73 Ta 74 W 75 Re 76 Os 77 Ir 78 Pt 79 Au 80 Hg 81 Tl 82 Pb 83 Bi 84 Po 85 At 86 Rn 87 Fr 88 Ra 89 Ac** 104 Rf 105 Db 106 Sg 107 Bh 108 Hs 109 Mt 110 Ds 111 Rg 112 Cn 113 Uut 114 Uuq 115 Uup 116 Uuh 117 Uus 118 Uuo Gas chromatography of (oxo)halides Gas chromatography of oxides (hydroxides) Gas chromatography of atoms in elemental state Liquid-liquid extraction Ion-exchange chromatography of (complex) anions Short history: Elements of interest - Gas phase and aqueous chemistry

TC of oxides and metals in a cryodetector channel made from PIN diodes covered with SiO 2, Al 2 O 3 or Au with α-decay and SF detection – COLD or COMPACT 2000 – now (Hs, Cn, 114, 113) TC of organometallic compounds in a cryodetector (tests for Sg, Bh, Hs, Mt) HI beam Target He Chemical reagent TC oven TC column TC peak IGC of (oxo)chlorides, bromides or oxide hydroxide in a quartz column with α-decay and SF detection – OLGA techniques + tape or wheel 1990s – 2000 (Rf, Db, Sg, Bh) 8 87 Fr 88 Ra 89 Ac** 104 Rf 105 Db 106 Sg 107 Bh 108 Hs 109 Mt 110 Ds 111 Rg 112 Cn 113 Uut 114 Uuq 115 Uup 116 Uuh 117 Uus 118 Uuo TC of (oxo)halides in a quartz column with detection of SF tracks in quartz or mica 1960s – 1996 (Rf, Db, Sg) Short history: Progress in the gas phase chemistry FUSHE Workshop 2012, , Weilrod GERMANY

SHE chemistry goals: Chemical identification of new SHE Discovery of new isotopes Investigation of decay properties – decay spectroscopy Proof of theoretical predictions Advantages of the gas phase chemistry: + fast, effective, easy to measure - limited number of compounds, Rn problem Goals of SHE chemistry and advantages of the gas phase chemistry FUSHE Workshop 2012, , Weilrod GERMANY

10 Thermochromatography Each atom reached a TC column is adsorbed and contributes to the measurement of chemical properties How to combine the advantages of both techniques? Thermochromatography (TC) and Isothermal chromatography (IC) Isothermal gas chromatography The measurement of specific decay chains after the chemical separation ensures the isotope identification FUSHE Workshop 2012, , Weilrod GERMANY

11 U. Kirbach et al., CTS, LBNL Berkeley, 2000 Ch.E. Düllmann et al., COLD, PSI/U Bern, 2001 TC cryo column/detector for alpha particles and SF …..for very volatile species only TC column = detection device FUSHE Workshop 2012, , Weilrod GERMANY

12 Synthesis and decay properties of superheavy nuclei Nuclear reaction studies in gas phase chemistry experiments FUSHE Workshop 2012, , Weilrod GERMANY

25 decay chains from 269,270,271 Hs were detected within 5 weeks Excitation function was 5 beam energies 13 Chemistry high sensitivity 266 Sg  360 ms SF 270 Hs ~23 s Sg 7 s 15 s 8.94; 8.84; Hs 9.7 s 8.95; Rf 78 s 3 s SF 267 Sg  1.5 m 8.20; SF 271 Hs ~4 s 9.13; Rf  8 s SF 1 pb level FUSHE Workshop 2012, , Weilrod GERMANY

? Group 12 and 14 Experimental sublimation enthalpies 87 Fr 88 Ra 89 Ac** 104 Rf 105 Db 106 Sg 107 Bh 108 Hs 109 Mt 110 Ds 111 Rg 112 Cn 113 Uut 114 Uuq 115 Uup 116 Uuh 117 Uus 118 Uuo Rn 14 Heavier and … more volatile Study of adsorption on a noble metal surface is preferable Calculated vs. experimental adsorption enthalpies and extrapolation for  H s FUSHE Workshop 2012, , Weilrod GERMANY

15 Gold covered detectors for TC and IC FUSHE Workshop 2012, , Weilrod GERMANY

48 Ca T=35°C liq. N 2 Getter Pump Sicapent ® Drying- unit Recoil- chamber Aerosol filter + getter Buffer COLD made by ITE (Poland) Gas flow Thermochromatography of the heaviest elements Hg (  ) Rn (  ) Actinide Target Model experiments! S. Soverna et al. Radiochim. Acta 2005 R. Eichler

Cn and E114 can be produced with cross sections similar to one of Hs, but…  E114 isotopes have half-lives of about 1 s only  High Rn background in 48 Ca induced reactions TC study of Cn/E114 FUSHE Workshop 2012, , Weilrod GERMANY

PSI-FLNR results Cn+114 ( ) (-21°C) (-21°C) (-39°C) (-28°C) (-28°C) (-5°C) (-5°C) (-4°C) (-4°C)gold ice(-124°C) (-88°C) (-88°C) (-90°C) (-90°C) (-93°C) (-93°C) Cn -25°C °C Rn -170°C Hg ~ 200°C << < < Pb ~1000°C (<<<) (-7°C) (-7°C) ΔH ads (E114 on Au) = kJ/mol (68%c.i.) ΔHads (Cn on Au) = kJ/mol (68%c.i.) No further events from E114 were detected in the later experiments in No events from E114 were detected in chemistry experiment at GFRS R. Eichler

48 Ca beam 0.4 particle  A 244 Pu rotating target 0.5 mg/cm 2 RTC COMPACT 2009: E114 chemistry at TASCA FUSHE Workshop 2012, , Weilrod GERMANY

Experimental setup Target: 244 PuO 2 Backing 2.5  m Ti Segment 1: 440  g/cm 2 Segment 2: 771  g/cm 2 Segment 3: 530  g/cm 2 Beam: 48 Ca +10 (5.475 MeV/u) TASCA / SIM RTC / COMPACT 20 FUSHE Workshop 2012, , Weilrod GERMANY

GSI results on E114 chemistry at TASCA Measured: COMPACT 1: 2 events COMPACT 2: 0 events Element 114 is a volatile metal Adsorption on gold is at least as strong as of Cn Pb >> Hg > 114  112 > Rn Low number statistics: 68% CI: COMPACT 1: 68.5% COMPACT 2: 31.5% Lower Lim:  H = -50 kJ/mol 95% CI: COMPACT 1: 37.8% COMPACT : 62.1% Lower Lim:  H = -48 kJ/mol Futher experiments on E114 chemistry are required FUSHE Workshop 2012, , Weilrod GERMANY

22 Target ( 249 Bk ;  0,5 mg/cm 2 ) SiO 2 - Ta 800°C (4  ) (4  ) He/Ar (70/30) Au pairs 2.5m 1 L/min On-going experiments: gas chromatography Studies of E113 produced as a daughter in 48 Ca induced reactions with 243 Am and 249 Bk First results are waiting for conformation experiments S. Dmitriev

Qin Zhi

New results of gas chromatography experiments with Db Qin Zhi

Is it possible to combine TC and IC advantages for less volatile compounds? PSI group probes diamond detectors suitable at higher temperatures FUSHE Workshop 2012, , Weilrod GERMANY

V(CO) 6 Cr(CO) 6 Mn 2 (CO) 10 Fe(CO) 5 Co 2 (CO) 8 Ni(CO) 4 Mo(CO) 6 Tc 2 (CO) 10 Ru(CO) 5 Rh 2 (CO) 8 W(CO) 6 Re 2 (CO) 10 Os(CO) 5 Ir 4 (CO) 12 Sg(CO) 6 Hs(CO) 5 Relativistic effects might be better pronounced Highly symmetric complexes with zero valent central metal atoms How to make volatile non-volatile elements? Organometallic compounds of d-elements FUSHE Workshop 2012, , Weilrod GERMANY J. Even

He CO MFC 3 Molecular sieve Pump TASCA MFC 1 MFC 2 RTC N 2(L) COMPACT 144 Sm( 24 Mg,4-5n) 163,164 W 152 Gd( 24 Mg,5-6n) 170,171 Os Gas chromatography studies of GSI, JGU, PSI, IMP FUSHE Workshop 2012, , Weilrod GERMANY J. Even

Os(CO) 5 -ΔHads: 43.5 kJ/mol W(CO) 6 -ΔHads: 46.5±2.5 kJ/mol Physisorption J. Even et al., J. of Inorg. Chem. (submitted) Tests with short-lived W and TASCA FUSHE Workshop 2012, , Weilrod GERMANY J. Even

Online Isothermal Vacuum Chromatography (i) PSI, R. Eichler et al. FUSHE Workshop 2012, , Weilrod GERMANY

Detectorbox (cooled PIN-Diodes/Peltier/Water) °C Ta - heat susceptor Induction coil chromatography column (25-500°C) pump vacuum chamber PIN diodes (Au covered?) Cu water cooling Mo-wire Oven 900K Cu liner chromatography column (SiO 2 ) Detector box scheme Online Isothermal Vacuum Chromatography (ii) PSI, R. Eichler et al. FUSHE Workshop 2012, , Weilrod GERMANY

Increasing beam intensity up to ~ 3E13 (cw GSI) Reliable target wheel systems   Use of a physical pre-separator  Combination of the chemical separation and detection in a one step – reactive detector surface for a chemical adsorption  New volatile compounds for cryo-TC of light transactinides  Vacuum chromatography for short-lived heavy transactinides New detector setups (also for decay spectroscopy) Most important technical developments for future chemical experiments with SHE FUSHE Workshop 2012, , Weilrod GERMANY

Near future experiments on gas phase chemistry of SHE Reliable experiment on E114 with higher statistics E113 gas phase experiment after pre-separator TC/IC of metal-carbonyles (Sg, Bh, Hs, Mt) TC/IC of metallocenes (Rf, Db,Hs) Decay spectroscopy after chemistry experiments (Sg, Hs) Search for n-rich isotopes of SHE produced in multinucleon transfer reactions Reaction mechanism studies Mass measurement of volatile SHE (compounds) ……. FUSHE Workshop 2012, , Weilrod GERMANY

Gas phase chemistry brings fruitful results in SHE studies Impressive developments in separation and detection techniques Problem: low production cross section for heavy transactinides  higher beam intensity + higher effectivity Problem: short lifetime for SHE Z>108  vacuum chromatography in metallic state New compounds for lighter SHE Collaborations for challenging experiments More beam time! Summary FUSHE Workshop 2012, , Weilrod GERMANY

NUSTAR Seminar

New Hs chemistry..and spectroscopy Hs 269   9.7 s Hs 270   20 s Hs 271   4 s NUSTAR Seminar

108 Hs 113 Uut s2d1s2d1 d - elements 243 Am( 48 Ca,3n)  (- α) (0.5 s) 284   0.48 s 113 First E113 chemistry: Study of volatility and adsorption on gold and/or an inert surface NUSTAR Seminar