Chemistry 6330 Autumn 2017 Midterm Exam Name: Ans wor k oo Question 1 pts / 25 pts Question 2: pts / 30 pts Question 3: pts/ 15 pts Question 4: pts / 30 pts TOTAL: PTS / 100 PTS aye = “Ih Zio -% cludeats ! 4 Higt= I go- 81 ~ 7! Loy) = 3” p14 - 8 « Go- 67 — 5 a so- ST 3 ety — S *Name: Ley (1) [25 pts] Consider a cyclic group of order = 8. (a) [8 pts} Build a group multiplication table for the group. elements: E,4,8,C,D,F,G,H + pr Cyce group: AY=B, A3=C, At: D ete... ’ : int ce cy ch) = Se PaME mp (ew & eg c DF GH e c FG@uUH 4 D @Hye 8 F HE OA c Ga ea B D 4 ABC F E B ¢ D 4G A c op F 8 enor G (b) [6 pts} Identify all the subgroups of the group. ts LE, D3 (2 fe, C13 in Ce pomt qup) te, B,D, G5 (= £6 %,G;/, Cy ¥in Cx pont qoup) Page 2Name: Key (©) [8 pts] Identify all the classes of the group (show your work) -Each cement is within its own Class ~ For each element X, tre similarity transform with al ofner elemunts of ie quaup, Y, ylelds the eumunt ¥, such that: Y"xY=x (@) [3 pts] Provide an example of a cyclic Point Group of order = 8 (an actual point group). ) The rotahonel group Ce —» cnsistsof E, Ce (m=l-F -only pure rotatiored quup) ore adic CS¢ i> onder example) Page 3Name: Koy (2) [30 pts] Consider the trans-MBr4Cly molecule shown below 5 + Gla Le Gero (a) [10 pts] Using the six halide atoms as basis set, write the matrices for the following operations using the halide numbering scheme and operations provided. (Cy = Cow rotation! C100 600 ' Lt COlooo]]2 3 Cy= |F 22 boof]3).ty 'oooool|ly|"]y 0°66 | ofls 5 0000 Oily v (ii) oy ©o! ob oo)fl 4 Oloodol2 2 100% O}]3],] 1 Oyv=|}0 00 1oo|\4 4 6 0001o6)]5 S 000001)\\v v (b) {6 pts] Write the representation (characters) that results from transposing the 6 halides in the molecule. Din [E24 Ce 2G) 26," 4 284 on Uv 20/204) foul AR 2 good 4 Page 4Name ___ Key (©) [10 pts} Is the representation in part (b) reducible? If so, reduce it and write it as a sum of irreducible representations of the group, We, it {> reducible , * ig = Yofurderedede sey] = 2 Arg BRag= Vie Turd #244 4] = O hig? Vey Ged a4eds BEY] = 1 Bg Y Bag = Wey b-Ye2-He4-% 4] =O #Eg = wef r-4-77 °° Heys Nef ia4erd = | Ex Ode We fusdeZe4-4- 8-4] 2 O ¥ Bowe Wu fusda 2-4-4 eee D> | Aru A Bio We futere4-4-Fe4 10 8Brus WW [u-H D-H e472 O Trades = 2Arg + Big + Aw + Eu (d) [4 pts] What is the relationship between the matrices in part (a) and those that give rise to the characters in the character table (those of the irreducible representations)? Could one arrive at one set of matrices from the other? If so, how? -They have Afferent basis sets = They can be transtormecl into one anotner trough a similarity transformation Page 5(3) LIS pts] Build the character table for the C,, point group. Show work and explain answers where necessary. 5 contain O Ando must WON) © rep: totally Symmes hel cas % actmogone| Exit a -\ 0 ee ener CP Use tre Great Ortnogonaltly Theorem .. - fe ire ducible Sum of the squares of damensions 6 ie represintations ih O Group raat equal Tae ovdler ¢ hu quup @ Sum of tne squares OF Me choaathers in Oay irreducible representation equals Te Orda 4 de Group The vectors made UP by chonacters of ailRerent 0 aoe repre sentotions are ormogmn “ sentation ne CHOAAA ES of ass WY PC dent. we ol matices \n a gen repre: : V e oor © fo Bek, sone as Tne num per of class<> ie Tae Same xotons. wrredudbe TERT son : =4\ so both A —=weed We Te in LD... cnovacker wader Cert) 7 ae Taker waines sbscn PRs Over|mrwbscrpt2 4.Name: (4) [30 pts] IF; exhibits the square pyramidal structurfpovg below. yn Pont qroeup= Cav (a) [5 pts] How many normal modes of vibrations are expected for IF,? Explain your answer normal mode> of vibration = 3N- ls unre N= numoor of atoms for Fg, Ne =? Ble)- ela s0 JA normed mode> of vibration iO (b) [10 pts} Derive Poa) (total degrees of motional freedom) and reduce it € 2C, Ci. Lov now, reduce Trot in Cav poink qwoup: une elie 4-24e Te 4 A Uae Me [ised <2 8-412 TAD aByeuefigedd -LA8-41 = 261 Were Velie -2- 841 = 182 Bee Vypausd l= 5 & Top “UD\ Pa 28, * Bt SE Page 7Name: — bey (©) [10 pts] What are the symmetries of the normal modes of vibration (I'y;,)? Show work. Tie = Got - Trot - Trans Frot > Rx Ry + Re from character table Frans > Xe y+ 2 From chorathor table Trot = E+ Ad Grons = Et Ay Gi = For - (etry - CE* Ay) Rin= 3A, +28, + Br* 3E (d) [5 pts] Which of the modes in part (c) are IR-active and which are Raman-active. Explain. IR aohve aT om for Wh, O24 AA XN from onocacker table fe = 3A, +E are IR achve A,tE Roman ochve for Roman, 6 = Mind Trin » onary Functions ‘eon character table Jaind * A+ Bit [Link] BN ,+20, + Brit 3E we Raman achve Page 8