A POSTCARD FROM THE ISLAND OF STABILITY: WHAT’S NEW IN SUPERHEAVY ELEMENT CHEMISTRY?

Prof. Dr. Andreas TürlerLabor für Radio- und UmweltchemieDepartement Chemie und BiochemieUniversität Bern

18.9.2017, APSORC17Jeju Island, South Korea

A postcard from the island of SHE

Session NC-2: Wed 20.9. 15:30 – 17:10

Plenary talks on the subject:

Prof. Y. Nagame, JAEA, Japan Tue 19.9. 09:00 – 09:30“Chemistry of the Heaviest Elements”

Prof. S. Dmitriev, FLNR, Russia,Fri. 22.9. 09:00 – 09:30“Superheavy Elements of the Mendeleev’s Periodic Table: Present Status and Future”

2

prot

on n

umbe

r

Meerenge der

Instabi-lität

sea of β+

instability

sea of β- instability

island of superheavy

nuclidesisland of

heavy nuclides

neutron number

20

50

82

114

20 82 126 184

peak of tin

peak of calcium

peak of lead

peak of uranium

radioactivitystrait

Weather report for the island of superheavy nuclides:disappearing fog and increasingly sunny!

The island of shell stabilized heavy nuclei

The island of superheavy nuclides!

The Periodic Table of the Elements

5

LanthanidesActnides

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu58 59 60 61 62 63 64 65 66 67 68 69 70 71

La57

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr90 91 92 93 94 95 96 97 98 99 100 101 102 103

Ac89

H

Li

Na

K

Rb

Cs

Fr Ra Ac

Ba

Sr

Ca

Mg

Be

Sc

Y

La

Ti

Zr

Hf

V

Nb

Ta

Cr

Mo

W

Mn

Tc

Re

Fe

Ru

Os

Co Ni Cu Zn Ga Ge As

Rh Pd Ag Cd In Sn Sb

Ir Pt Au Hg Tl Pb Bi

Rf Db

B C N O F

Al Si P S Cl

Se Br

Te I

Po At87 88 89-103 104 105

55 56 57-71 72 73 74 75 76 77

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53

78 79 80 81 82 83 84 85

19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35

11 12 13 14 15 16 17

3 4

1

5 6 7 8 9

1

2

3 4 5 6 7 8 9 10 11 12

13 14 15 16 17 He

Ne

Ar

Kr

Xe

Rn

54

86

36

18

10

218

Sg106

Bh107

Hs108

Mt109 110

Ds111

Rg112 113 114 115 116 117 118

Cn Fl Lv

6d107s2 6d107s27p1/22 7s27p1/2

Nh Mc Ts Og

Nihonium (Nh), Z=113

6

209Bi(70Zn, 1n)278Nh, 3 atoms observed!

Prof. Kosuke MoritaRIKEN, Japan

Moscovium (Mc), Z=115

7

Flerov Laboratory of Nuclear Reactions, Dubna. Moscow region

243Am(48Ca, 3-5n)286-288Mc, >100 atoms observed!

Tennessine (Ts), Z=117

8

249Bk

High Flux Isotope Reactor (HFIR, Oak Ridge)~25 mg 249Bk

249Bk(48Ca, 3,4n)293,294Ts, >20 atoms!

Oganesson (Og), Z=118

9

Prof. Yuri Tsolakovich Oganessian, Flerov Laboratory of Nuclear ReactionsDubna, Moscow region

249Cf(48Ca, 3n)294Og, 4 atoms observed!

10

Metal-carbonyl complexes-

a new class of compounds for transactinide chemistry

experiments

RIKEN Wako (J)H. HabaD. KajiY. KomoriN. SatoK. MoritaK. MorimotoS. Yano

JAEA Tokai (J)M. AsaiY. KaneyaA. MitsuakiY. NagameT. SatoA. ToyoshimaK. Tsukada

U Mainz (D)A. Di NittoCh.E. DüllmannK. EberhardtJ.V. KratzL. LensN. Wiehl

HIM Mainz (D)J. Khuyagbaatar

GSI Darmstadt (D)E. JägerJ. KrierV. PershinaA. Yakushev

PSI Villigen (CH)R. DresslerR. EichlerD. PiguetA. Vögele

U Berne (CH)A. TürlerN. ChieraB. Kraus

The CO Collaboration 2016

IMP Lanzhou (PRC)F. FanZ. QinY. Wang

Reimei Partner InstitutionY. Nagame, Ch.E. Düllmann, and R. Eichler for the CO Collaboration – Gas phase chemistry of Sg(CO)6 – JAEA Tokai, Japan – March 10, 2017

Niigata Univ. (J)K. Ooe

Transactinide metal carbonylsvolatility and stability

12

Mainz – GSI – PSI – Bern – Berkeley – Tokai – Riken – Lanzhou collaboration

Carbonyl experiments at GARIS/RIKEN

13

1 2 m0

RIKEN/GARIS

Gas-jet transport system

D2Q2Q1D1

EVRs

He/CO

0 100 mm

33 Pa

144Sm(24Mg,4-5n)163,164W248Cm(22Ne,5n)265Sg

COMPACTN2(L)

Sg(CO)6 a superheavy carbonyl complex

14

H. Haba et al., Phys. Rev. C85, 024611 (2012)

Assessing thermodynamic stability

15

Theory [1]

Experiment [3]

Mo W Sg168 193 204

169 192 ???

168 193 181

First Bond Dissociation Energy(FBDE), kJ/mol

[1] C. S. Nash, J. Am. Chem. Soc. 121 (1999) 10830.[2] M. Ilias, V. Pershina, Inorg. Chem. 56 (2017), 1638.[3] K. E. Lewis, D.M. Golden, G.P. Smith, J. Am. Chem. Soc. 106 (1984) 3905.

Theory [2]

Bonding in carbonyl complexes

TM backbonding

LUMO

TM donation

HOMO Influence ofrelativity!

C.S. Nash et al., J. Am. Chem. Soc. 121 (1999) 10830

Decomposition studies: Mo(CO)6 + W(CO)6

16

100 200 300 400 500 600

0

20

40

60

80

100

Experiment Mo(CO)6: 1.2 l/min 0.3 l/min

Sur

viva

l pro

babi

lity,

%

Temperature, C 100 200 300 400 500 600

0

20

40

60

80

100

Experiment W(CO)6: 1.0 l/min 2.0 l/min

Sur

viva

l pro

babi

lity,

%

Temperature, C

Mo

W

I. Usoltsev et al., Radiochim. Acta 104,141 (2016).

T~100K

FBDE = 25 kJ/mol

COMPACTN2(L)

D2Q2Q1D1

25 – 800°CSilver/Quartz column

Two-step decompostion model: M(CO)6

17

I.Usoltsev et al., Radiochim. Acta 104, 531 (2016).

desorption

adsorptionads ~ exp(‐Hads/RT)

Decomposition model: Mo(CO)6 + W(CO)6

18

100 200 300 400 500

0

20

40

60

80

100

Exp. 1.2 l/minExp. 0.3 l/min MCS 0.3 l/min MCS 1.2 l/min

FDBE = 168 KJ/molA = 8.6E5

Sur

viva

l pro

babi

lity,

%

Temperature, C

K.E. Lewis et al., J. Am. Chem. Soc. 106, 3905 (1984)

300 400 500 600

0

20

40

60

80

100

Exp. 1 l/min Exp. 2 l/min

MCS 1 l/min MCS 2 l/min

FDBE = 192 KJ/molA = 8.6E5

Sur

viva

l pro

babi

lity,

%

Temperature, C

Shaded Area is 1 interval of AShaded Area represents a variation of

-∆Hads within typical experimental uncertainty of ±4 kJ/mol

The bond dissociation is almost not activated:

dec ~k*T/h*A* exp(-FBDE/RT)

Mo W

I.Usoltsev et al., Radiochim. Acta 104, 531 (2016).

Prediction of Sg(CO)6 Decomposition

19

100 200 300 400 500 600

0

20

40

60

80

100

Exp. Mo(CO)6 Exp. W(CO)6

Simulation for Sg(CO)6 (A = 8.6E5) FBDE intervals: 204 ± 8 kJ/mol[1]

181 ± 4 kJ/mol[2]

Sur

viva

l pro

babi

lity,

%

Temperature, C- Clearly the FBDE dominates the predicted experimental behavior, therefore the experimental approach can deliver sensitive results for FBDE

[1] C.S. Nash, B.E. Bursten, J. Am. Chem. Soc. 121, 10830 (1999).[2] M. Ilias, V Pershina, Inorg. Chem. Inorg. Chem. 56, 1638 (2017).

Outlook to vacuum chromatography

-faster, cleaner, higher

temperatures

PhD thesis P. Steinegger (UniBE)R. Eichler, R. Dressler, D. Piguet (PSI)M. Schädel, Y. Nagame et al. (JAEA)

Isothermal Vacuum Chromatography (IVAC)

DetectorHeat source (e.g. resistance oven)

Read-outelectron.

300 350 400 450 500 550 600 650 700 750 800 850

100 %

0 %

Temp [⁰C]

Yield

[%] -Hads = 150 kJ / mol

-Hads = 170 kJ / mol

-Hads = 160 kJ / mol

Vacuum Chromatography features:

• No particulate transport (no aerosol formation) → lowerbackground

• Clean stationary surfaces

• Good energy resolution for alpha particle detection

• Fast technique

The IVAC system

in-b

eam

mon

itor

Quartz insert

Hf hot catcher

Heat shields

quartz chromatography column

isothermaloven

start-/ end-oven

4-fold diamond detector

read-out

IVAC of 184Tl (T1/2 = 9.7 s)

Page 23

Vacuum Chromatography of SHE 113, 115, & 116

24

Shutter

Hot catcher Diamond detectorProduct beam from separator

Acknowledgements

‐ We thank the ion source and accelerator staff at the RIKEN Nishina Center for providing intense and stable ion beams.

‐ The present work is partially supported by:¥ the Reimei Research Program (Japan Atomic Energy Agency);

€ the German Federal Ministry for Education and Research contract 06MZ7164;

€ the Helmholtz association contract VH‐NG‐723; 

¥ the Ministry of Education, Culture, Sports, Science, and Technology, Japan, Grant‐in‐Aids 19002005 and 23750072; 

₣  the Swiss National Science Foundation contract 200020_144511; 

¥(元/圆) the National Natural Science Foundation of China (grant 11079006).