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3.091 – Introduction to Solid State Chemistry Lecture Notes No
3.091 – Introduction to Solid State Chemistry Lecture Notes No

... together” by comparable energies. The “strength” of the bonds can obviously vary from system to system with the nature of the electronic rearrangement. Even the inert gases, particularly the heavier ones like xenon, are capable of forming associations with other atoms. Sometimes we find that two ato ...
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... • Bond lengths and angles of "normal" organic molecules quite accurate (within 2%) • Conformational energies accurate to 1–2 kcal/mol. • Vibrational frequencies for most covalent bonds systematically too high by 10–12% • Zero point vibrational energies: ~1-2 kcal/mol • Isodesmic reaction energies ac ...
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... seem not to follow the rules. Click on the ‘Real Molecules’ tab, we will be looking at: HL only - SF6, PCl5, XeF4, BrF5, SF4; HL and SL – CH4, BF3, CO2, SO2, NH3, H2O. For each one: a. Click and drag to have a good look at the three-dimensional shape b. Draw what you see (in three dimensions where r ...
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SEMESTER 1 EXAM Prblms/Short Ans

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Bent's rule



Bent's rule describes and explains the relationship between the isovalent hybridization of central atoms in molecules and the electronegativities of substituents. The rule was stated by Henry Bent as follows: ""Atomic s character concentrates in orbitals directed toward electropositive substituents"".The chemical structure of a molecule is intimately related to its properties and reactivity. Valence bond theory proposes that molecular structures are due to covalent bonds between the atoms and that each bond consists of two overlapping and typically hybridised atomic orbitals. Traditionally, p-block elements in molecules are assumed to hybridise strictly as spn, where n is either 1, 2, or 3. In addition, the hybrid orbitals are all assumed to be equivalent (i.e. the n+1 spn orbitals have the same p character). Results from this approach are usually good, but they can be improved upon by allowing hybridised orbitals with noninteger and unequal p character. Bent's rule provides a qualitative estimate as to how these hybridised orbitals should be constructed. Bent's rule is that in a molecule, a central atom bonded to multiple groups will hybridise so that orbitals with more s character are directed towards electropositive groups, while orbitals with more p character will be directed towards groups that are more electronegative. By removing the assumption that all hybrid orbitals are equivalent spn orbitals, better predictions and explanations of properties such as molecular geometry and bond strength can be obtained.Bent's rule can be generalized to d-block elements as well. The hybridisation of a metal center is arranged so that orbitals with more s character are directed towards ligands that form bonds with more covalent character. Equivalently, orbitals with more d character are directed towards groups that form bonds of greater ionic character.
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