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 --- --- --- --- --- ---
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:
*
"
58
Ce
90
Th
59
Pr
91
Pa
60
Nd
92
U
61
Pm
93
Np
62
Sm
94
Pu
63
Eu
95
Am
64
Gd
96
Cm
65
Tb
97
Bk
66
Dy
98
Cf
67
Ho
99
Es
68
Er
100
Fm
69
Tm
101
Md
70
Yb
102
No
71
Lu
103
Lr
s and d p1/2 orbitals bit l are
stabilized / contracted
Rel. effects ~Z
2) Indirect relativistic effect:
2 � Pronounced in heavy elements
-the color of Au:
Au: �E (5d conduct. band � Fermi): 2.4 eV (in vis)
Ag: g �E (4d ( conduct. band � Fermi): ) 3.5 eV (in ( UV) )
2) Indirect relativistic effect:
Other orbitals (p3/2, d, f) are
better shielded from nucleus
� ddestabilized t bili d / expanded d d
-the "inert pair" effect: stabilized 6s electron pair
reduces valency: Tl(I), not Tl(III); Pb(II), not Pb(IV),...
-high ox.states of light actinides: expanded 5f orbitals
available for chemical bonding: U(VI) [but no Nd(VI)]
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