Inorganic Chemistry
5th Edition
ISBN: 9780321811059
Author: Gary L. Miessler, Paul J. Fischer, Donald A. Tarr
Publisher: Prentice Hall
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Chapter 5.4, Problem 5.12E
Determine the reducible representation for all the
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Set up the secular determinants for (i) azulene (3), (ii) acenaphthylene (4) within the Hückel approximation and using the out-of-plane C2p orbitals as the basis set.
The FEMO theory of conjugated molecules is crude and marginally better results are obtained with simple Huckel theory. (a) For a linear conjugated polyene with each of N carbon atoms contributing an electron in a 2porbital, the energies Ek of the resulting π molecular orbitals are given by:
Ek = α + 2β cos kπ/N+1 k = 1,2,3, ... N
Use this expression to estimate the resonance integral β for the series consisting of ethene, butadiene, hexatriene, and octatetraene given that ult raviolet absorptions from the HOMO, which is a bonding π orbital, to the LUMO, which is an antibonding π* orbital, occur at 61 500, 46 080, 39 750,and 32 900 cm- 1, respectively. (b) Calculate the π-electron delocalization energy, Edelcc = Eπ -n(α + β). of octatetraene, where Eπ, is the total π-electron binding energy and n is the total number of π-electrons.
What irreducible representations do the four H1s orbitals of CH4 span? Are there s and p orbitals of the central C atom that may form molecular orbitals with them? In SiH4, where 3d orbitals might be available, could these orbitals play a role in forming molecular orbitals by overlapping with the H1s orbitals?
Chapter 5 Solutions
Inorganic Chemistry
Ch. 5.1 - Repeat the process in the preceding example for...Ch. 5.2 - Prob. 5.2ECh. 5.3 - Use a similar approach to the discussion of HF to...Ch. 5.4 - Sketch the energy levels and the molecular...Ch. 5.4 - Using the D2h character table shown, verify that...Ch. 5.4 - Using orbital potential energies, show that group...Ch. 5.4 - Prob. 5.7ECh. 5.4 - Prob. 5.8ECh. 5.4 - Prob. 5.9ECh. 5.4 - Use the projection operator method to derive...
Ch. 5.4 - Determine the types of hybrid orbitals that are...Ch. 5.4 - Determine the reducible representation for all the...Ch. 5 - Expand the list of orbitais considered in Figures...Ch. 5 - On the basis of molecular orbitals, predict the...Ch. 5 - On the basis of molecular orbitals, predict the...Ch. 5 - Compare the bonding in O22,O2 and O2 Include Lewis...Ch. 5 - Although the peroxide ion, O22 and the acetylide...Ch. 5 - High-resolution photoelectron spectroscopy has...Ch. 5 - a. Prepare a molecular orbital energy-level...Ch. 5 - a. Prepare a molecular orbital energy-level...Ch. 5 - NF is a known molecule a. Construct a molecular...Ch. 5 - The hypofluorite ion, OF can be observed only with...Ch. 5 - Prob. 5.11PCh. 5 - Although KrF+ and XeF+ have been studied, KrBr+...Ch. 5 - Prepare a molecular orbital energy level diagram...Ch. 5 - Methylene, CH2 plays an important role in many...Ch. 5 - Beryllium hydride, BeH2 is linear in the gas...Ch. 5 - In the gas phase, BeF2 forms linear monomeric...Ch. 5 - For the compound XeF2 do the following: a. Sketch...Ch. 5 - TaH5 has been predicted to have C4v symmetry, with...Ch. 5 - Describe the bonding in ozone, o3 on the basis of...Ch. 5 - Describe the bonding in SO3 by using group theory...Ch. 5 - The ion H3+ has been observed, but its structure...Ch. 5 - Use molecular orbital arguments to explain the...Ch. 5 - Prob. 5.23PCh. 5 - Prob. 5.24PCh. 5 - The isomenc ions NSO (thiazate) and SNO...Ch. 5 - Apply the projection operator method to derive the...Ch. 5 - Apply the projection operator method to derive the...Ch. 5 - A set of four group orbitals derived from four 3s...Ch. 5 - The projection operator method has applications...Ch. 5 - Although the cl2+ ion has not been isolated, it...Ch. 5 - BF3 is often described as a molecule in which...Ch. 5 - SF4 has C2v symmetry. Predict the possible...Ch. 5 - Consider a square pyramidal AB5 molecule. Using...Ch. 5 - Prob. 5.34PCh. 5 - For the molecule PCl5 : a. Using the character...Ch. 5 - Molecular modeling software is typically capable...Ch. 5 - Prob. 5.39PCh. 5 - Calculate and display the orbitals for the linear...Ch. 5 - Prob. 5.41PCh. 5 - Prob. 5.42PCh. 5 - Prob. 5.43PCh. 5 - Diborane, B2H6 , has the structure shown. a. Using...
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- What is the point group resulting from adding the inversion operation to C2v ?arrow_forwardConstruct a Frost circle for a planar eight-membered ring with one 2p orbital on each atom of the ring and show the relative energies of its eight π molecular orbitals. Which are bonding MOs, which are antibonding, and which are nonbonding?arrow_forwardBy using FMO (orbital coefficients and delta EHOMO-LUMO), ALSO sizes of molecules, explain the regioselectivity .arrow_forward
- Take the four hydrogen 1s orbitals of CH4 and determine how they transform under Td. b) Confirm that it is possible to reduce this representation to A1 + T2. c) With which atomic orbitals on C would it be possible to form MOs with H1s SALCs of symmetry A1 + T2?arrow_forwardSet up the secular determinants for (i) linear H4, (ii) cyclic H4 within the Hückel approximation.arrow_forwardProvide possible molecular structures for NbF5 with C4v and D3h point groupsarrow_forward
- Use the matrix representatives of the operations σh and C3 in a basis of 2pz orbitals on each atom in BF3 to find the operation and its representative resulting from C3σh. Take z as perpendicular to the molecular plane.arrow_forwardMake a list of all symmetry operations present in Bh3 and H2O?arrow_forwarddeduce the irreducible representation of 4 chlorine 3p orbitals of PtCl42 - which are perpendicular to the plane of the moleculearrow_forward
- Consider the ClO4 – anion. Use symmetry analysis to determine the orbitals used in bonding by the central atom. (a) As a consequence of the multiple Cn axes with n > 2, the pi bonding cannot be separated into perpendicular and parallel components as was done with SO3. Rather these orbitals must be operated on together, an inseparable pair.arrow_forwardIs the electron density consistentwith equal contributions from the tworesonance structures for O3? Explain.arrow_forwardThe point group for a square pyramidal geometry is C4v. Assign the nine s, p, and d orbitals to their correct irreducible representations (i.e., Mulliken Symbols) in C4v point group.arrow_forward
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