CHEM 153 - Advanced Inorganic Chemistry PROBLEM SET 2 (due ...

3. The 5 K luminescence spectrum of trans-[Re(O) 2 (pyridine) 4 ]I is shown below, along with a table ofpeak positions. The luminescence lifetime at 5 K is about 7 s.a. Construct a ligand-field (LF) diagram for D 4h trans-[Re(O) 2 (L) 4 ] + (L is anuncharged donor ligand ) using the following orbitals: five metal 3d orbitals,one set of four ligand orbitals, and a 2p + two 2p orbitals for each oxoligand.b. Determine the frequencies and suggest assignments for the vibrationalmode(s) giving rise to the fine structure in the spectrum.c. Perform a Franck-Condon analysis of the vibrational fine structure in theluminescence profile and determine what S HR -value(s) give the best fit to theobserved spectrum.d. Rationalize the vibronic structure in this band on the basis of an assignment forthe electronic transition giving rise to the luminescence.PeakPosition(cm 1 )16 78416 57316 36415 87715 66615 46014 97214 76414 56114 07313 86613 66813 17812 97412 78312 28612 09111 91111 40011 21111 028