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• Provide explanations for the number of intense perchlorate Cl-O stretching vibrational modes observed in the IR of the following three silver(I) complexes.

1. a) The perchlorate anion in Ag(NH₃)₂(ClO₄) has a single intense Cl-O stretching   vibrational mode observed by IR at 1170cm^-1.

1. b) The IR of Ag(NH₃)ClO₄ has three Cl-O stretching vibrational modes at 1220 cm^-1,1130 cm^-1and 920 cm^-1 observed in the IR .

1. c) The IR of AgClO₄ has four Cl-O stretching vibrational modes at 1210 cm^-1,1140 cm^-1, 1040  and 910 cm^-1 observed in the IR .

• The gas phase cobalt(II) free ion has a ⁴F ground term which in an octahedral ligand field splits into ⁴T_1g (-0.6 Δ_o– CI) , ⁴T_2g(+0 .2 Δ_o) and⁴A_2g(+1,2 Δ_o ) electronic states.

1. How many micro states are contained inthe ⁴F ground term of gas phase cobalt(II)  free ion  and the⁴T_2g electronic state for an octahedral cobalt(II) complex ?

1. What is the ground state for a tetrahedral  cobalt(II) complex ?

3. Provide an explanation for the difference in effective magnetic moments between K₂[CoCl₄] (μ_eff(298K) = 3.9β)  and K₄[CoCl₆] (μ_{eff (298K)}= 5.0β) .         (β = electron Bohr Magneton)

1. What are the Δ_oand CI values for an octahedral  Co(II) complex that has ligand field transitions at  Δν₁ =7,400cm^-1 (⁴T_2g←⁴T_1g) and Δν₂ =15,400cm^-1 (⁴A_2g←⁴T_1g) ?

• Vanadium tetrachloride (VCl₄ )is a bright red colored liquid with a vapor pressure of 5×10-² torr at 298K.

1. Briefly discuss why the standard state of VCl₄ is a liquid and VCl₂ is an ionic solid?

1. How many microstates are in the gas phase V⁴⁺ free ion ground term and the V⁴⁺ free ionground J state ?

1. How many microstates are present in the ground electron configuration and ground electronic state for VCl₄ assuming tetrahedral symmetry ?

1. State the Jahn Teller Theorem  and briefly discuss whether or not VCl_4(g) is expected to manifest aJahn Teller effect .

1. What is the expected orbital angular momentum in the ground

state of VCl_4(g) ?

1. The molar magnetic susceptibility (χ_m) at 298K is +1130×10^-6 cm³mol^-1 .

What is the effective magnetic moment for VCl₄ at 298K and does this μ_efffulfill the expectations forVCl₄ ground state in Td symmetry ?

1. Use the electric dipole transition selection rules to show whether or not the ligand field ( d→d ) transition(s) for VCl₄are spin and orbitally allowed as pure electric dipole transitions assuming T_d

1. Write down the irreducible representations for VCl_4(g) translations , rotations  and  vibrations assuming T_d