Glenn T. Seaborg and the Modern Periodic Table of Elements. V. Pershina GSI, Darmstadt, Germany

Transcription

1 Glenn T. Seaborg and the Modern Periodic Table of Elements V. Pershina GSI, Darmstadt, Germany

2 Glenn T. Seaborg ( ) 1997 [

3 Periodic Table of Dimitri I. Mendeleev Dimitri I. Mendeleev and the Table of 1869 the Table of 1904

4 Atomic Structure and Periodic Table Rutherford - (scattering of alpha-particles by heavy nuclei) determination of nuclear charge Z A 1913 Moseley (x-ray spectral lines Z) and Meyers - properties vary periodically with Z (atomic number) 1923 Bohr proposed that the periodicity in properties might be explained by the electronic structure. Bohr model of atom: (n + l) 1925 Pauli's four quantum numbers (n, l, m l and m s ) and his exclusion principle

5 Atomic Structure and Periodic Table 1926 Schrödinger equation - three quantum numbers: n, l and m l examination of atomic spectra electron configurations are determined experimentally 8s 8p 9s 1926 (1936) empirical Madelung's rule (Klechkowski) : n+l

6 Henry D. Hubbard Periodic Chart of 1924 The American classic one went through 12 editions (1936)

7 [

8 "Actinide concept" of Glenn T. Seaborg , Chicago: discovery of two more elements Am (95) and Cm (96) by separation chemistry based on the "actinidie concept" "I was warned at the time that it was professional suicide to promote this idea, which has since been called one of the most significant changes in the periodic table since Mendeleev s 19th century design," Seaborg wrote, but he held to his convictions [

9 Periodic Table of Glenn T. Seaborg Glenn T. Seaborg had "written one of the most brilliant pages in the history of discovery of chemical elements" G. T. Seaborg, Nobel Lecture, December 12, 1951]

10 Development of ab initio Theory 1926 Schrödinger equation Ĥ Ψ = E Ψ E T = Ψ Hˆ Ψ Ψ Ψ 1928 Dirac equation H = H = 1 2 ˆ 2 Z r + 1 i i i i< j rij icα ( k) ( k) β( k) c ˆ 2 + k k k< j rij Z r 1 Wave-function 1928 Hartree (Coulomb) (SCF) 1933 Hartree-Fock (exchange) Ψ = ϕ i 2 Ψ = ( N!) 1/ ϕ1(1) ϕ1(2)... ϕn ( N)

11 History of ab initio Atomic Relativistic Calculations 1935 first rel. (num.) calculations for atoms with more than 2 electrons (HF Dirac-Fock formalism: Swirles, UK) 1940 relativistic (Hartee) SCF calc. on Cu (Williams, US) 1959 revolution in micro-electronic 1960 rel-c. calc. (Hartree) on Fe, Pt,... U (Cohen, CF) (IBM704) 1960 Grant: analytical integration and SCF equations for spinors DHF and Dirac-Slater calculations Coulthard (Melb.), Nestor, et. al. (Oak Ridge), Libermann, Waber, Cromer, et. al. (CF, Los Alamos) (Z= ) Desclaux (F), Greiner, Fricke (G) (till Z=173) Hermann and Skillman (Z < 103) (non-rel.) Periodic Table of Fricke, Greiner and Waber

12 Electronic Configurations of Transactinides d 2 7s 2 6d 3 7s 2 6d 4 7s 2 6d 5 7s 2 6d 6 7s 2 6d 7 7s 2 6d 8 7s 2 6d 9 7s 2 6d 10 7s 2 7s 2 7p 1 7s 2 7p 2 7s 2 7p 3 7s 2 7p 4 7s 2 7p 5 7s 2 7p 6 E, ev 119 8s s 2?? np 3/2 9s 1/2 ns 1/2 np 1/2 8d 3/2 Electronic configurations of elements [118] + 8s Element Seaborg Goldanski (1968) Waber, et al. Seaborg (1969) Fricke, Waber (1971) Madelung DS DF 121 7d 7d 8p 1/ g 2 7d 2 7d8p 1/ g 3 6f 1 7d 2 6f7d8p 1/ g 4 6f 3 7d 1 6f 3 8p 1/2-60 Ge Sn Pb Z 125 5g 5 5g 1 6f 3 7d 1 5g6f 3 8p 1/ g 6 5g 2 6f 3 7d 1 5g 2 6f 2 7d8p 1/2

13 Periodic Table of Fricke, Greiner and Waber 9p1/2 8p3/2 9s 34 elements: 8p1/2+ 7d + 5g(18) + 6f(14) [B. Fricke, W. Greiner and J. T. Waber, Theor. Chim. Acta 21, 235 (1971)]

14 Periodic Table of Glenn T. Seaborg (transactinides and superactinides) 32 elements: 5g(18) + 6f(14) [O. L. Keller, Jr., and G. T. Seaborg, Ann. Rev. Nucl. Sci., 27, 139 (1977)]

15 Modern Atomic Relativistic ab initio Methods - Dirac-Coulomb-Breit H h B D DCB = hd ( i) + i i< j ij ( i) = = cαp + βmc (1/ r + V nuc 2 [ αiα j + ( αirij)( α 2rij) / rij ]/ rij ij + B ij ) - 4c wave-functions (Slater, Gauss., numer.) φ nkm = ϕ ϕ P = Q i nk ( r) Υ r ( r) Υ r nk km ( r, ξ ) ( r, ξ km ) - Electron correlation (beyond DHF)

16 Beyond Dirac-Fock: Electron Correlation Configuration interaction (CI) CIS, CISD, CISDT Ψ = k =1 c ψ k k MCSCF (MCDF) Ψ = k ' = 1 u= 1 c k ' c u ϕ u MBPT 0 H ˆ = Hˆ + Hˆ (1) Coupled Cluster (rel. in 1980) CCSD(T) FSCC, IHCC, etc. Ψ = 2 S exp( S) Ψ0 = 1+ S Ψ 2! 0

17 Electronic Configurations of Lr and Rf Ground states in various approximations Element DF MCDF DCB + CC Lr 6d7s 2 7s 2 7p 1/2 7s 2 7p 1/2 Rf 6d 2 7s 2 6d7s 2 7p 1/2 6d 2 7s 2 DF: Fricke, Waber, Desclaux, et al. ( 1970) MCDF: Desclaux, Fricke, Johnson, Glebov, et al. ( ) DCB CC: Eliav, Kaldor, et al. (1994, 1995)

18 Electronic Configurations of the Superactinides at Different Levels of Theory 119 8s 120 8s 2 [118] + 8s Elem. Madelung DS DF MCDF (AL) DCB CC Seaborg (1968) Waber (1968) Fricke (1971) Nefedov (2006) Eliav (1998) 121 7d 7d 8p 1/2 8p 8p 122 5g 2 7d 2 7d8p 1/2 7d8p 1/2 7d8p 1/ g 3 6f 1 7d 2 6f7d8p 1/2 6f 2 8p 1/ g 4 6f 3 7d 1 6f 3 8p 1/2 6f 2 8p 2 1/ g 5 5g 1 6f 3 7d 1 5g6f 3 8p 1/2 5g6f 2 8p 2 1/ g 6 5g 2 6f 3 7d 1 5g 2 6f 2 7d8p 1/2 5g 2 6f 3 8p 1/2...? n + l rule no correlation with correlation

19 Periodic Table of Pyykkö MCDF calculated electronic configurations Z q El. conf f f g g g g s 2 5g s 2 5g 16 8p s 15 g g 18 6f p 4 [P. Pyykkö, PCCP 13, 161 [2011]] 18 elements: 5g(18) : superlanthanides

20 Periodic Tables of Elements till Z=172 based on (MC) Dirac-Fock Calculations Fricke 165 Seaborg 166 Pyykkö ,140, (8p,7d,6f,5g)

21 A Higher Accuracy: QED Effects Main contributions to Lamb shift: electron self-energy (SE) vacuum polarization (VP) nuclear finite size (FS) ΔS α ( αz) = 3 π n 4 F( αz) m c e 2 F (αz ) = F + F + SE VP F FS [P. Pyykkö, et al., Phys. Rev. A 57, R689 (1998)]

22 Influence of Electron Correlation and QED Effects on Atomic Properties IP and EA (in ev) of Cn and element 118 in various approximations Element DF DF + DFB + DCB + CC + CC CC QED IP(112) (0.023) EA(118) (0.006) CC: E. Eliav, et. al. PRA, 52, 2765 (1995); E. Eliav, et. al. PRL 77, 5350 (1996); I. Goidenko, et al. PRA 67, (R) (2003) QED: C. Thierfelder and P. Schwerdtfeger, PRA 82, (2010)

23 Electronic Configuration of E140 correlation QED Method Ground state Ref. Year high-sectors FSCC possible! Eliav soon MCDF (OL) + QED 5g 15 8p 4 6f (?) Indelicato 2011 MCDF (AL) 5g 14 6f 3 7d8p 2 Nefedov 2006 MCDF (AL) 5g 16 8p 2 (2+) Pyykkö 2011 DF 5g 14 6f 3 7d8p 2 Fricke 1971 DF 5g 18 7d 3 Nefedov 2004 level of theory MCDF(OL) are restricted due to computer limitations [P. Indelicato, Theor. Chem. Acc. 129, 495 (2011)]

24 The End of the Periodic Table MCDF + Breit + QED calculations confirmed the end of the PT with Z = 173 [E(1s) < -2mc2] Z = [P. Indelicato, et al. Theor. Chim. Acta 129, 495 (2011)]

25 Future Periodic Table of the Elements? Z=173 Placement of elements in the PT will be more difficult and the structure not simple