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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.


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  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 .


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  • The gas phase cobalt(II) free ion has a 4F ground term which in an octahedral ligand field splits into 4T1g (-0.6 Δo– CI) , 4T2g(+0 .2 Δo) and4A2g(+1,2 Δo ) electronic states.


  1. How many micro states are contained inthe 4F ground term of gas phase cobalt(II)  free ion  and the4T2g electronic state for an octahedral cobalt(II) complex ?



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


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  1. Provide an explanation for the difference in effective magnetic moments between K2[CoCl4] (μeff(298K) = 3.9β)  and K4[CoCl6] (μeff (298K)= 5.0β) .         (β = electron Bohr Magneton)



  1. What are the Δoand CI values for an octahedral  Co(II) complex that has ligand field transitions at  Δν1 =7,400cm-1 (4T2g4T1g) and Δν2 =15,400cm-1 (4A2g4T1g) ?



  • 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 VCl4(g) is expected to manifest aJahn Teller effect .


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

state of VCl4(g) ?



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

What is the effective magnetic moment for VCl4 at 298K and does this μefffulfill 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 Td



  1. Write down the irreducible representations for VCl4(g) translations , rotations  and  vibrations assuming Td

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