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Actinide contraction

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(Redirected from Actinoid contraction) Decrease of ionic radii across the actinide series
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The actinide contraction is the greater-than-expected decrease in atomic radii and ionic radii of the elements in the actinide series, from left to right.

Description

It is more pronounced than the lanthanide contraction because the 5f electrons are less effective at shielding than 4f electrons. It is caused by the poor shielding effect of nuclear charge by the 5f electrons along with the expected periodic trend of increasing electronegativity and nuclear charge on moving from left to right. About 40-50% of the actinide contraction has been attributed to relativistic effects.

A decrease in atomic radii can be observed across the 5f elements from atomic number 89, actinium, to 102, nobelium. This results in smaller than otherwise expected atomic radii and ionic radii for the subsequent d-block elements starting with 103, lawrencium. This effect causes the radii of transition metals of group 5 and 6 to become unusually similar, as the expected increase in radius going down a period is nearly cancelled out by the f-block insertion, and has many other far ranging consequences in post-actinide elements.

The decrease in ionic radii (M) is much more uniform compared to decrease in atomic radii.

Element Atomic electron
configuration
(all begin with )
M electron
configuration
M radius (pm)
(6-coordinate)
Ac 6d7s 5f 111
Th 6d7s 5f
Pa 5f6d7s 5f
U 5f6d7s 5f 103
Np 5f6d7s 5f 101
Pu 5f7s 5f 100
Am 5f7s 5f 99
Cm 5f6d7s 5f 99
Bk 5f7s 5f 98
Cf 5f7s 5f 98
Es 5f7s 5f
Fm 5f7s 5f
Md 5f7s 5f
No 5f7s 5f
Lr 5f6d7s 5f

References

  1. Seth, Michael; Dolg, Michael; Fulde, Peter; Schwerdtfeger, Peter (June 1995). "Lanthanide and Actinide Contractions: Relativistic and Shell Structure Effects". Journal of the American Chemical Society. 117 (24): 6597–6598. doi:10.1021/ja00129a026. ISSN 0002-7863.
  2. Laerdahl, J. K.; Fægri, K.; Visscher, L.; Saue, T. (1998-12-22). "A fully relativistic Dirac–Hartree–Fock and second-order Mo/ller–Plesset study of the lanthanide and actinide contraction". The Journal of Chemical Physics. 109 (24): 10806–10817. Bibcode:1998JChPh.10910806L. doi:10.1063/1.477686. ISSN 0021-9606.
  3. Chistyakov, V. M. (1968). "Biron's Secondary Periodicity of the Side d-subgroups of Mendeleev's Short Table". Journal of General Chemistry of the USSR. 38 (2): 213–214. Retrieved 6 January 2024.
  4. Housecroft, C. E.; Sharpe, A. G. (2004). Inorganic Chemistry (2nd ed.). Prentice Hall. pp. 536, 649, 743. ISBN 978-0-13-039913-7.
  5. Cotton, F. Albert; Wilkinson, Geoffrey (1988), Advanced Inorganic Chemistry (5th ed.), New York: Wiley-Interscience, pp. 776, 955, ISBN 0-471-84997-9
  6. Jolly, William L. Modern Inorganic Chemistry, McGraw-Hill 1984, p. 22


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