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Question 133

Which of the following factors may be regarded as the main cause of lanthanide contraction?

Solution

The lanthanides correspond to the filling of the $$4f$$ subshell from $$Ce$$ to $$Lu$$. With each step, one proton is added to the nucleus and one electron enters the $$4f$$ subshell.

Shielding (or screening) power of electrons depends on the type of orbital: $$s \gt p \gt d \gt f$$. Thus, $$4f$$ electrons are the poorest at shielding each other from the increased nuclear charge.

Because $$4f$$ electrons lie deep inside the atom, any new $$4f$$ electron added does not sufficiently repel or shield the other $$4f$$ electrons from the nucleus. As a result, the effective nuclear charge $$Z_{\text{eff}}$$ felt by the outer electrons rises steadily along the series. This increasing $$Z_{\text{eff}}$$ pulls all electron clouds slightly closer to the nucleus, causing a gradual decrease in atomic and ionic radii known as lanthanide contraction.

Other suggested factors—such as shielding of $$5d$$ electrons by $$4f$$ electrons—play only a minor role because $$5d$$ orbitals are scarcely populated during the main part of the lanthanide series. The dominant cause remains the self-shielding inefficiency within the $$4f$$ subshell itself.

Hence the principal reason for lanthanide contraction is:
Option A which is: Poor shielding of one $$4f$$ electron by another in the same subshell.

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