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Inorganic Chemistry: Study Guide – Exam 2 – Fall 2015 Study Guide – Suggested Topics A periodic table will be given. Bring a calculator. Prerequisite concepts from General Chemistry 1 & 2, Quantitative Analytical, and Organic I/II Chapter 1 Fundamental particles of an atom Atomic number, mass number, notation Relative atomic mass and isotopes, weighted average mass spectroscopy and isotopes isotope and allotrope quantum theory/wave mechanics Relationships between energy, speed of light, wavelength, frequency Emission spectra of H (Lyman, Balmer, Paschen) Bohr’s theory of the atom Wavemechanics and wave-particle duality Uncertainty principle Wavefunction, probability, Schrodinger eq. o radial, angular parts of wavefunction o normalization Atomic orbitals and quantum numbers o allowed values of quantum numbers, sets of quantum numbers o degenerate o labels o number of orbitals o shapes, sizes of orbitals o angular momentum, spin-orbit coupling o ground state, excited state electron configurations Interactions in multi-electron atoms Relative energies of orbitals in neutral atoms Shielding, screening, effective nuclear charge o Slater’s rules Periodic Tables, group names aufbau principle Pauli exclusion principle Valence and core electrons o Representations of electronic configurations, E diagrams Ionization energies and electron affinities o Trends, exceptions Chapter 2 Valence Bond (VB) theory and Molecular Orbital (MO) Theory Lewis Structures VB - homonuclear, heteronuclear molecules o shortcomings diamagnetic, paramagnetic Covalent bond distance, covalent radius, van der Waals radius Molecular Orbital Theory o Linear combinations of atomic orbitals (LCAOs) o bonding, antibonding, nonbonding molecular orbitals o overlap integral o symmetry labels, parity o centrosymmetric, noncentrosymmetric o bond order o schematic representations of atomic orbitals, molecular orbitals o basis set o orbital overlap o orbital mixing o sigma-pi crossover, photoelectron spectroscopy o symmetry allowed interactions o MO diagram, E levels, effective nuclear charge o HOMO, LUMO Octet rules, exceptions to octet rule Isoelectronic species Electronegativity o definition, trends Dipole moments VSEPR o stereochemistry o ranking of repulsions, 1X, 2X, 3X bond o valence electrons, core electrons o structures o electron domain, molecular geometry, bond angles o coordination numbers o limitations o stereochemically active, inactive Isomerism o Stereo: optical, geometric cis-, trans fac-,mer-, axial, equatorial o Structural: coordination, ionization, linkage Chapter 3 Symmetry a. Symmetry operation b. Symmetry elements vi. Identity vii. Symmetry plane (h, d, v) viii. Inversion center ix. Proper axis x. Improper axis Point Groups a. Characterizes a molecule by including all of its symmetry operations b. Use flow chart to determine point group of a molecule Character Table a. Each point group has its own character table b. Column headings are the symmetry operations c. Horizontal rows are the irreducible representations d. First column contains the symmetry labels e. Last two columns contain info about the vectors, atomic orbitals, IR and Raman activity. If a symmetry label is associated with an x, y or z in the column to the right of the characters, it is IR active. If a symmetry label is associated with a product term in the farthest right right column of the table, it is Raman active. Degrees of freedom: A molecule containing N atoms has 3N degrees of freedom (translational, rotational, vibrational). a. Linear molecules have 3N-5 degrees of vibrational freedom b. Non-linear molecules have 3N-6 degrees of vibrational freedom For a vibration to be IR active, there must be a change in the molecular dipole moment. For a molecule to be Raman active there must be a change in the net polarizability tensor. Centrosymmetric molecules obey the rule of mutual exclusion. Assigning symmetry labels to vibrational modes a. If the vibrational mode is known and illustrated, sketch the resulting vibrational mode before and after each symmetry operation of the point group. Using the character table, assign the symmetry label and identify if the mode if IR and/or Raman active. Determining the symmetries of vibrational modes and if the modes are IR and/or Raman active a. Determine how many atoms are left unchanged by each symmetry operation. Find the reducible representation and reduce into the irreps. Remove translational and vibrational modes… Identify which modes are IR and/or Raman active and how many.… Determining the symmetries of the stretching modes if they are IR and/or Raman active a. Determine how many bonds are left unchanged by each symmetry operation. Find the reducible representation and reduce into the irreps. Identify which are IR and/or Raman active and how many.… Developing a character table a. Determine the effect of each symmetry operation on the x, y, z translation and the rotation Rx, Ry, and Rz. The resulting set of characters correspond to an irrep in the character table. Note: The list of topics is not exhaustive and there may be questions on a topic covered in lecture or the textbook that is not listed above.