Name, CHM3920 Quantum Chemistry Exam #1 * Useful information * Jsin?bxe de = [:- sah), momentum operator }, Gao 2 Je rot) of ae 25, San (mm and nare integers) sin asin 8 = Foosta~ f)~Leosla+ p); Jeosthx) ae =F sin); A= 6.626 «10 $s; c=2.998 x 10° m/s; 1 eV = 1.602 x 10" J; m,=9.10 x 10! kg. Answer all the questions on this paper. Clearly show all work and units and use the correct number of sig. figs otherwise you will lose credit. Remember, if you can't do the problem write down as much as you can that is of relevance to solving the problem (to get partial credit). 1. Use the free electron model to calculate the wavelength (in nm) of the lowest energy electronic transition for the negatively charged species H1C=CH-CH=CH-CH;. You can assume that each (C=C bond is 1.35 A long and each C-C bond is 1.54 A long. Include a carbon atom radius at each end ofthe box. Hint be careful withthe total numberof x electrons. (10 points) o.mk 384 Tice hom eryrn 2 2le8) 4 2Cuse) +208) = 232A =e Se CU mew ne ce) tz Ceo TS chay) =e Te. —e tks 4b 3 3 DE=he tt % Sx tt 2 A he ened _: Ae - j@ -3) ie m4 tone” Ry a — 2 E32K Om \ Bae Hh wre xto Te \ i Den 3 (estes Fs) a gtixw ys fe peel’, 20.2) Ooo"2. A sodium lamp emits light of $89.0 nm. Calculate: (a) the frequency of the light (2 points) A =SFAL OKI im Ne ee ere Slice! a $39.6 nto Vm = 5.040 «ta s1 We 5.610 =i “st Ge) (b) the wavenumber of the light (2 points) ee eee = (G9V7FFAS Src ln 10cm DH. GBS x toon a (c) the energy of the photons (express your answer in J and eV) (3 points) : 34 Wer SELLE IO Ts x T04Cx1o''s7 e=hv = 2.105ev. C= 3.373 uw ty (@ the momentum of the photons (3 points) no (© state whether the photon is sufficiently energetic to cause electrons to be emitted when this light falls on cesium metal (work function of Cs metal is 2.140 eV). If not, explain why. Ifit is, calculate the kinetic energy of the ejected electrons (in eV) (3 points) nevi Frome of Cs 2 2IGGeY = Lilodsey, re tH me Pe Cregg of ploien wm er The he yoreGy) (b) Prove that the yz wavefunction is normalized. Show and explain all work. (10 points) (2) Ger octtojeralh, we acut be a Fi \ 3, (a) Prove that the particle in a box wavefunctions -(2) wo(2) and Y= ase orthogonal. Standard integrals are given atthe start of the exam paper. ae = (* Ya a Ole) (Ba Wig Mages S(t) Soles) (5) So Gan oC GF men = D> SCRTHOG EAS (b) Neee Sed] cet ch San (Smel new te ver] Se ZS) | = [| a NcRmauced4. A particle ina one-dimensional infinite potential well isin the m= 1 state. Calculate the probability ‘thatthe particle will be located in the range 0.5a < x < 0.75a where a is the width ofthe well Recall the particle in a box wave function is y, = (2) so(22) (10 points) ean “Dianne, = je aes G ory Rene Oe Fectiy paris He ye heme Freeneiay of ; 6. 4o4 Go ewer WI) oe psa ¢ & Fe 45. A particle is constrained to move in a one-dimensional box between x = a and x=. The potential energy is such that the particle cannot be outside these limits and the wavefunction is given by =A //x where A is a real normalization constant, Determine the value of the normalization constant A. @ points) New, ee yer Suce Wis new « A “(e] sw As (oh) b- Ba, 6. The terms state and level are not synonymous in quantum mechanics, For the particle in a cubic box (@ = =c) consider the energy range E <(15/"/ 8ma”). This range contains 6 energy levels which comprise a ‘otal of 17 states. Explain this and account for all the energy levels and states using the appropriate quantum numbers. (8 points) a aks ger LE Osmeeng <1 Ee Bb [cles a an Bast. wt fk poe . al on e= oh Bsiews i 2 i Saat _ _ ZB sew § she. Bsmes7. State whether cach of the following statements is TRUE or FALSE. Provide a clear explanation for your answer and state the correct answer if the statement is FALSE. (a) The particle in a box ground state has = 0. (2 points) Cave nel & lowes Ce Ghee ee For eee Move TE ase Yeo eyes se SES (b) The maximum probability density for the particle in a box will becomes less localized (i.e. it begins to spread out more evenly over the entire box) as the value of 7 increases. (2 points) Teve ey is jeer the Beier correspon pane & (©) For the n = 2 state of the particle in a box, the probability of finding the particle in the left quarter of the box is the same as the probability of finding the particle in the right quarter of the ae we the appropriate wavefunction and probability distribution). (4 points) ee Aah a ee 2 7 bee nm \ las leg (@) The general expression ( A ee ) which must be satisfied for an operator to be Hermitian may be writen in Dirac bracket notation as (m| Arn) =(n| A m) 3 points) TBE gmlaled = Puta ¥, Lola\ny’ = Jef AUS fle, aren! = J }¥/ar @ points) (©) The expectation value (B) of property B is always calculated using (B) ise 1 8 News {BD = § er RW odie oy opemtes(9 The value ofthe commutator [4, 8] (where 4 = Sand = x° (multiply by x2) is 2x. 3 ie paints) [ABy- 48-8 ABE = 4 BAC - wae so [AR -Aafea2ef Se tis 6 acd o& A988 CT aivedd both E gor ston you work). As nation u's cactwally False I guat (g) The integral needed to calculate the average linear momentum of a particle in a box (between x= Oand x= a) for the n= 2 state is given by (p,) -2y i ind si 2 i pois Ese -tha & oe “fey OX las ee tN WS a ¢| = 2xt + df Soeaee PAL Heat's ornthn are th 1s miele! (h) The wavelength of light absorbed for the particle in a box transition for level n —> (n+1) will increase as the quantum number n increases. (2 points) Fae ae : Leen ab cme PIB Creqay ret, caps Yorn Onn Ste Hoh as nT, ian bebe cwljacenr Ceres ® Go ne 4) Show \ fe CO bRuscke bebe thee Comair | FF co swe AE=HE YY AG TAAL ee Bend Be. yn ben aegis mr