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The lanthanide contraction is the greater-than-expected decrease in atomic radii and ionic radii of the elements in the lanthanide series, from left to right. It is caused by the poor shielding effect of nuclear charge by the 4f electrons along with the expected periodic trend of increasing electronegativity and nuclear charge on moving from left to right.
The lanthanide contraction, i.e. the reduction in size of the Ln 3+ ion from La 3+ (103 pm) to Lu 3+ (86.1 pm), is often explained by the poor shielding of the 5s and 5p electrons by the 4f electrons. [18] Lanthanide oxides: clockwise from top center: praseodymium, cerium, lanthanum, neodymium, samarium and gadolinium.
The lanthanide contraction only partially accounts for this anomaly. [11] Because the 6s 2 orbital is contracted by relativistic effects and may therefore only weakly contribute to any chemical bonding, Hg–Hg bonding must be mostly the result of van der Waals forces. [11] [13] [14] Mercury gas is mostly monatomic, Hg(g).
The effect of the lanthanide contraction can be observed in the REE behaviour both in a CHARAC-type geochemical system (CHArge-and-RAdius-Controlled [40]) where elements with similar charge and radius should show coherent geochemical behaviour, and in non-CHARAC systems, such as aqueous solutions, where the electron structure is also an ...
Due to the effects of the lanthanide contraction, the decrease in ionic radii in the lanthanides, they are very similar in properties. Vanadium is somewhat distinct due to its smaller size: it has well-defined +2, +3 and +4 states as well (although +5 is more stable).
This is an effect of the lanthanide contraction: the expected increase of atomic radius from the 4d to the 5d elements is wiped out by the insertion of the 4f elements before. Titanium, being smaller, is distinct from these two: its oxide is less basic than those of zirconium and hafnium, and its aqueous chemistry is more hydrolyzed. [ 28 ]
The trivalent lanthanide ions decrease steadily in size from lanthanum to lutetium, an effect known as the lanthanide contraction. [31] From lanthanum to dysprosium , the coordination number is maintained at 9 with a tricapped trigonal prismatic structure, although starting from samarium the capping water molecules are no longer equally ...
The d-block contraction is less pronounced than the lanthanide contraction but arises from a similar cause. In this case, it is the poor shielding capacity of the 3d-electrons which affects the atomic radii and chemistries of the elements immediately following the first row of the transition metals, from gallium (Z = 31) to bromine (Z = 35). [19]