Superheavy Element Research Superheavy Element Research

The Periodic Table and Relativity
1 18
1 2
H 2 13 14 15 16 17 He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 13 14 15 16 17 18
NNa MMg 3 4 5 6 7 8 9 10 11 12 Al Si P S Cl AAr
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57+* 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs
87
Ba
88
La
89+"
Hf
104
Ta
105
W
106
Re
107
Os
108
Ir Pt Au Hg
112
Tl Pb Bi Po At Rn
Fr Ra Ac Rf Db Sg Bh Hs 109 110 111 Cn 113 114 115 116 117 118
Mt Ds Rg --- --- --- --- --- ---
* 58 59 60 61 62 63 64 65 66 67 68 69 70 71
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
" 90 91 92 93 94 95 96 97 98 99 100 101 102 103
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
Rel. effects ~Z2 Element 114, � member Pronounced in group in heavy 14: elements
-the -Electronic color of Au: conf.: [Rn] 7s
Au: �E (5d conduct. band � Fermi): 2.4 eV (in vis)
Ag: �E (4d conduct. band � Fermi): 3.5 eV (in UV)
2 6d10 5f14 7p 2
1/2
-"Quasi-closed g ( shell" configuration g ) due ( to )
relativistic p
-the "inert pair" 1/2 subshell closure
effect: stabilized 6s electron pair
reduces Evident valency: question: Tl(I), not Tl(III); Pb(II), not Pb(IV),...
-high metallic t ox.states lli (Pb (Pb-like) lik of light )bbehavior, actinides: h i or expanded 5f orbitals
available noble-gas for (Rn-like) chemical bonding: behavior? U(VI) [but no Nd(VI)]
Examples of relativistic orbitals
p1/2 p 3/2
s p d f
RRelativity l ti it in i Chemistry Ch i t
Electrons near nucleus:
v is a large g fraction of c
� relativistic mass increase
1) Direct relativistic effect:
s and d p1/2 orbitals bit l are
stabilized / contracted
2) Indirect relativistic effect:
Other orbitals (p3/2, d, f) are
better shielded from nucleus
� ddestabilized t bili d / expanded d d
3) Spin-orbit splitting:
Heavy atoms: two states per l
� p1/2/p3/2; d3/2/d5/2; f5/2/f7/2 Ch.E. Düllmann – Superheavy element research – FIAS Colloquium – Frankfurt Institute for Advanced Studies, Frankfurt – October 20, 2011