Celebrating 150 years Periodic Table Historical remarks and current situation

1. Celebrating 150 yearsPeriodic Table • Historicalremarksandcurrentsituation • Heinz W. Gäggeler • Department of Chemistry & Biochemistry, University of Bern, Switzerland • and • Paul Scherrer Institut, Villigen, Switzerland

2. D.I. Mendeleev

3. Outline • Fewcomments on the CV of D.I. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Whatsnext?

4. Dimitry Ivanovich Mendeleev (8.2.1834 - 2.2.1907) (1) • Born in Tobolsk (Siberia) • Elementary schools in Tobolskfollowedbystudies at Main Pedagogical Institute St. Petersburg • 1859 - 1861: Leaveto Western Europe [Heidelberg, Bonn, Paris] • 1861 : 1st Int. Chemical Congress in Karlsruhe • 1867: Full Professor of General Chemistry at St. Petersburg University. Start writing a freshmanchemistrycoursetextbook • 17. Feb. 1869: «An attempt at a systemoftheelementsbased on theiratomicweightandchemicalanalogues»

5. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

6. First Periodic Table from 1869

7. Second Periodic Table from 1871

8. Predictions by Mendeleev in 1871 lead to the following discoveries • Eka-Al: Discoveredby P.E. Lecoq de Boisbaudran in 1875, namedGa • Eka-B: Discoveredby L.F. Nilson in 1879, namedSc • Eka-Si: Discoveredby C. Winkler in 1886, namedGe • The two Swiss elements: • Yb (1878) & Gd (1880): Discoveredby J-Ch G. de Marignac in Geneva

9. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

10. Discovery of noble gases (1) • 1868: Jules Janssen discovered a newline at 587.49 nm in the solarspectrumwhich he assignedto a «solar metal» . Suggestedname Helium (Helios forsun and -iumfor a metal) . Assumption: thisnewelementexistsonly on thesun. • 1882: Luigi Palmieriidentifiedthisline also in lavafrom Vesuv. • 1895: William Ramsey identifiedHeas gas emanatingfrom an uraniummineraltreatedwithsulfuricacid . • 1894-1898: William Ramsey & colleaguesdiscoveredNe, Ar, Kr and Xefromfractionateddestillationofair. • 1904: William Ramsey receives noble prizefordiscoveryof noble gases • 1899: Ernest Rutherford discoveredemanating gas fromuranium andthoriumminerals. Latercalled Radon (Rn)

11. Discovery of noble gases (2) • 1999: Viktor Ninov and colleaguesannounceddiscoveryeka-Rn at LBNL (PRL publication). 2002: retracted due tofalsifieddata! • 2006: Yuri Ts. Oganessian and colleaguesclaimedtohavediscoveredeka-Rn at FLNR in Dubna in a heavy ionfusionreaction. On 30 Dec. 2015 officiallyacceptedby IUPAC. On 8 June 2016 IUPAC announcesthenameOganesson (Og) forthiscurrentlyheaviestelement. • General rule: Namesfor noble gase elements end with –on. Exception: heliumforhistoricalreasons

12. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

13. Marie Curie‘sobservation: pure uraniumislessradioactivethanpitchblendewith an equivalentamountofuranium. Whichelementsarehidden in pitchblende? • 1898:discoveryofpoloniumandshortlyafterwardsradiumby P. & M. Curie • 1899: discoveryofradonby Rutherford • 1902: discoveryofAcbyGiesel • 1917: discoveryofprotactiniumby Hahn and Meitner andindependentlyby Soddy andCranston • 1939: discoveryoffranciumbyPerey • 1940: discoveryofastatineby Corso, McKenzie and Segre

14. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

15. Periodic Table 1934 from G. Herrmann, Radiochimica Acta, 70/71, 52 (1995)

16. Seaborg’sfailuretodiscover Pu aseka-Os after bombarding U withdeuterons & neutrons.Seaborg’ssuggestionfor an actinideseries (1945)

17. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

18. Idea • Isneutronflux in an hydronuclear bomb sufficiently high toproduce heavy elements via captureofmanyneutronsby238U followedby a b-decaychain? • 1stthermonuclearexplosion IVY/MIKE on 1 Nov. 1952 • 238U (15n;7b)253Es & • 238U(17n;8b)255Fm • discovered in bomb debris after chemicalseparation (a-HIB separation on CIX column)

19. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

20. The heaviestelementdiscoveredpurelybychemicalmeans: Mendelevium (1955) • → Synthesis: bombardmentof253Es witha-particles.→ Collection ofproducts in a foil. → Separation ofproducts after dissolutionoffoil on a cationexchangecolumnwitha-HIB

21. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

22. Shell stabilisation spherical deformed Courtesy: S. Hofmann

23. Stability against spontaneous fission exp. liq. drop

24. Twotypesof heavy ionfusionreactionstoproduceNoandheavierelements •  Cold fusion: thesuccessstory at GSI todiscoverelements 107 (bohrium, Bh) through 112 (copernicium, Cn).Target: 82Pb or83Bi; Projectile: 25Mn - 30Zn (Minimum excitationenergy@fusionbarrier:  10 – 20 MeV) •  Hot fusion: discoveryofNo (102) – Sg (106) and Nh (113) – Og (118) Target: 94Pu – 98Cf; Projectile: 11B, 12C, 22Ne; 48Ca (Minimum excitationenergy at fusionbarrier:  30 - 40 MeV)

25. Howphysicists separate newelements and howtheyidentifysingleatoms On-Line separators at an accelerator Twotypes: • - Wien filtervacuumseparators • - Gas filledmagneticseparators Identificationofseparatedatoms (ions) Position sensitive silicondetectorstoassaya-decaychains

26. SHIP @ GSI-Darmstadt

27. Velocity filter SHIP: the device used to discover elements 107 (bohrium) through element 112

28. Gas-filled magnetic separators @ LBNL(Berkeley), FLNR (Dubna), GSI (Darmstadt) and RIKEN (Japan)

29. BGS Schematic

30. 277Cn a1 11.45 MeV 280 ms 273Ds a2 11.08 MeV 110 ms 269Hs a3 9.23 MeV 19.7 s 265Sg a4 4.60 MeV (escape) 7.4 s 261Rf a5 8.52 MeV 4.7 s 257No a6 8.34 MeV 15.0 s Howtoidentifysingleatomsof a newelements Example: 208Pb(70Zn,1n)277Cn Known nuclides SHIP@GSI 9.2.1996 22:37 Currentdetectionlimit: approx. oneatom per year Courtesy Sigurd Hofmann, GSI

31. Excitation functions for production of isotopes of element 114 (Fl) in 242,244Pu+48Ca reactions pb (10-36cm2)

32. Why are production rates so low? 248Cm(26Mg, 5n)269Hs (Z=108) 26Mg 248Cm FUSION 274Hs* 269Hs 10 hours beam 1 mg/cm2 1 billion 1 surviving atom Courtesy: A. Türler

33. Riken and Dubnadiscoveriesduring last 20 yearsusing70Zn & 48Ca inducedfusionreactions • 70Zn + 209Bi → 278113 (Nh) (worldrecord, 1-2 atoms/year!)48Ca + 242,244Pu → 288,290114 (Fl)48Ca + 243Am → 288115 (Mc)48Ca + 248Cm → 293116 (Lv)48Ca + 249Bk → 294117 (Ts)48Ca + 249Cf → 294118 (Og) 249Cf istheheaviesttargetavailable in mg amounts

34. Transactinidenuclei (status 2019) Courtesy Robert Eichler

36. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Whatsnext?

37. Single atomstudiesof heavy elements • All elementsheavierthan Fm areavailableonly at a singleatomlevel. Nomacrochemicalproperties but onlymicrochemicalpropertiescanbedetermined. • Gas phaseseparationtechniques: abletoisolateproducts and depositthemcontinuously on surfaceskept at different temperatureswithinaboutonesecond

38. Reactionsused and numberofatomsfound in the„firsteverchemicalstudies“ for Z ≥ 106 (Sg) • Seaborgium (Z=106); (GSI Darmstadt; IC)248Cm( 22Ne;5n)265Sg (T1/2 = 7 s); 7 atoms (M. Schädel et al., Nature, 388, 55 (1997)) (a) • Bohrium (Z=107); (PSI Villigen; IC)249Bk(22Ne;4n)267Bh (T1/2 = 17 s); 6 atoms (R. Eichler et al., Nature, 407, 64 (2000)) • Hassium (Z=108); (GSI Darmstadt; TC)248Cm(26Mg;5n)269Hs(T1/2 = 15 s); 7 atoms (C.E. Düllmann et al., Nature, 418, 860 (2002)) (a) • Copernicium (Z=112); (FLNR/JINR Dubna, TC)242Pu(48Ca,3n)287Fl (T1/2 = 0.5 s)283Cn (T1/2 = 4 s); 2 atoms (R. Eichler, Nature, 447, 72 (2007)) (a) • Nihonium (Z=113); (FLNR/JINR Dubna, TC)243Am(48Ca; 2,3n) 288,289Mc  284,285Nh; 5 atoms (S.N. Dmitriev et al., Mendel. Comm., 24, 253 (2014) • Flerovium (Z=114): (FLNR/JINR Dubna; TC)242,244Pu(48Ca; 3,4n)287,288Fl (T1/2 = 0.5 s; 0.8s): 3 atoms (R. Eichler et al., Radiochim. Acta. 98, 133 (2010) (a) • (a) Confirmed in independantexperimentsthoughsometimeswith different chemicalcompounds

39. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • The uraniumdecayproducts: birthofradiochemistry • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Einstein’sinfluence on Mendeleev’sprinciple. • Whatsnext?

40. Relativistic effects • contractionandstabilizationofsandp1/2orbitals (direct rel. effect) • expansionanddestabilizationofp3/2, dandforbitals (indirect rel. effect) • SO splittingofp, d, forbitals j = l s scale as ~ Z2

41. Influenceofrelativisticeffects on calculatedcohesive (sublimation) energiesforgroup 14 elements E, eV Leftblackarrow: withoutspin-orbit splittingRightblackarrow: withspin-orbit splitting A. Hermann, P. Schwerdtfeger, H.W. Gäggeler et al. 2010

42. News from TAN 2019, Wilhelmshaven (25.-30.8.2019) Eka Radon – Oganessonis a semiconductor! J.-M. Mewes, O. Rosette, P. Jerabek, & P. Schwerdtfeger Angew. Chem, Int. Ed. (in print)[10.1002/anie.201908327]

43. Outline • CV of D.M. Mendeleev • The firstperiodictableanditsconsequences • Noble gases: a newgroupofelements • Seaborgs suggestion: theactinides • The nuclearweaponselements • The failureofchemiststodiscovernewelementsbeyondatomicnumber 101 (Md) • Howphysicistsdiscoveredtheelementsaboveatomicnumber 101 (Md) upto 118 (Og) • Howchemistsstudyelements at a fewatomlevel • Whatsnext?

44. Periodic Table today

45. Outlook • Experiments plannedtoproduceelement 120 atFLNR (reaction50Ti+249Cf) andstarted at RIKEN(54Cr+248Cm) • Howtoreachtherealcenteroftheislandof superheavy elements • Whatistheheaviestelementthatcanbechemicallyinvestigated?

46. CourtesyYu.Ts.Oganessian

47. Periodic Table tomorrow Pekka Pyykkö, Chem. Phys. Phys. Chem, 13, 161 (2011)