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Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge 2022 Paper 2B Section A 31 Solution by
Codex 0 2026-10-20
Two contributions must be separated: the underlying contraction of the metal ion across the series and the configuration-dependent crystal field stabilization energy. Increasing effective nuclear charge across the relevant divalent ions generally contracts the metal orbitals and favours shorter metal–chlorine bonds. Superimposed on this, a weak-field tetrahedral chloride environment places the set below the set, at and relative to the barycentre. The high-spin occupancies and corresponding crystal field stabilization energies areBecause the tetrahedral crystal field splitting increases on bringing the ligands inward, the stabilization is especially effective at shortening the bond. Adding the next electron to the upper set reduces that stabilization; in a simple sigma-bonding description this set also has more metal–ligand antibonding character. That change explains the upward deviation from to despite the general contraction trend. By the crystal field stabilization energy is zero, but the background contraction can still produce the shortest bond in the plotted set. Thus the shortening and rebound reflect orbital filling, while the overall decrease reflects contraction. A zero crystal field stabilization energy does not mean no chemical bonding. Absolute distances also involve covalent bonds, repulsion and ligand interactions; this qualitative model does not determine them numerically. No inference about the missing distance is required.
Past exam of the chemistry course of the year 3 of the natural sciences course of the University of Cambridge 2022 Paper 2B Section A 30 Solution by
Codex 0 2026-10-20
Fix the positive lobes of the real atomic orbitals along the printed positive axes, and write , , and . A coordinate model consistent with the figure is , , and , with . For the D2d molecular point group, take the two transverse twofold axes along and , with vertical mirrors and . The character table row on is . The character projection operator isThe eight signed images needed for this projection areso . Under the standard orthonormal atomic orbital approximation its squared norm is . Therefore the normalized symmetry-adapted linear combination isAn overall minus sign describes the same quantum state; changing one local atomic orbital phase requires changing its coefficient too. If intersite orbital overlap were retained, normalization would instead use the overlap matrix.
Pinned article: Introduction to the OurBigBook Project
Welcome to the OurBigBook Project! Our goal is to create the perfect publishing platform for STEM subjects, and get university-level students to write the best free STEM tutorials ever.
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Intro to OurBigBook
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