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Problem Set #4 (Chem 1113A W'07, due Thu. 02/08/07 at 11:053m, 100pts) Name: â€˜\ V Forming study groups is permissible, but you must construct your solutions independently. By writing down my name, i conï¬rm that I strictly obey the academic ethic code when doing this problem set. Please write down the names of
everyone who you worked with on this problem set under your name. (i) Seven questions, one for each day. As a â€œpunishmentâ€ to the classâ€™ impressive performance, no extra credit
question this time. (ii) Please write out algebraic details and arguments. if you use math formulas or literature values, please cite
your source(s). (iii) Please include these few pages as the cover sheet for your solutions. (iv) If you have difficulties/questions, please ï¬nd resources and assistance ASAP. (v) Academic ethics need to be strictly obeyed. No exceptions! Please refer to the syllabus. A. Basic Material (Textbook) [1] Preview #11 (due 02/02/07 Fri., deferred to 02/05/07 Mon. due to SE#1)
[2] Preview #12 (due 02/05/07 Mon.) [3] Preview #13 (due 02/07/07 Wed.) [4] PlB1D (35 rats)
(a) .5 Consider a particle in a onetâ€™iimcnsional box deï¬ned
Ilâ€™tx) z 0, a > x > 0 and VUâ€˜) r: so. x 2 a. x S 0, Explain why
git of the following unnormalizcd functions is or is not an â€™. ptabtc wave function based on criteria such as being
â€˜nsittent with the boundary conditions, and with the u iatton of tiftxkfxtï¬‚dx with probabiiity. rm:
.AcosMâ€” c. Cx3(x mo) .42...
sinUthza)
(Hint: check if the given wavefunction satisfies the BCs and the 7 Max Born conditions on Lecture Note #13 15. (b)
P433 The funcï¬on #10:) m Axli  (x/aï¬‚ is an acceptable A > : jg) 3;â€œ L; LL. 5. {,3 .
wave function for the particle in the onedimensional inï¬nite â€œ' I
depth box of length 0 Calculate the normalization constant 4 and the expectation values (A) and 0:3 )
(c) Once we know the wavefunction at a specific time, we can extract valuable infomation about the quantum systems at that time. First example, if the quantum system happens to be In an eigenstate. Please change
â€œ rom 0. 31a to 0. 35aâ€ to â€œfrom 0.3a to 0.4aâ€. :8 Cal culatc the probability that a panicte m a one
iensional box of length a is found between 0.3m and
5a when it is described by the lâ€™oitowing Wave functions: â€˜ ,2 . (17.x 3â€œ? â€˜ _ r . .1 y â€˜
â€œSin 2.. 2, , L i: ' 4 ~ ,
â€˜a , a J " â€œ L â€™ ._Â§ X ';.B(x+ x1} cl. Q 77 .5â€œ? â€œâ€œâ€™ mex 'â€œ â€˜L 53â€˜. in;
5
â€A
xÂ»
it?
w
\ï¬
!
l"
\ would you expect for a classicat pmticlcâ€˜? Compare your
{malts in the two cases with the classical result.  ' is a more complete and general theory, and can be used to describe both microscopic and
. ' acroscopic systems. Letâ€™s use â€œparticle in a 30 box" for example. Please change the edge length from
' '1nn1 to 10nm. P423 Generally, the quantization of translational morion is
not signiï¬cant for atoms because of their mass. However. this
conclusion depends on the dimensions of the space to which
they are conï¬ned. Zeolites are structures with small pores that
we describe by a cube with edge length 1 nm. Calculate the
energy of a 112 molecule with n;r = n, = n.T h= lO.Con1pare
this energy to Hal T = 300 K. 15 a classical or a quantum
description appropriate? (b) Please change the temperature T from 298K to 398K. P422 This problem explores under what conditions the
classical limit is reached for a macroscopic cubic box of edge
length a. An argon atom of average translational energy 3/2 H
is conï¬ned in a cubic box of volume V = 0.500 m3 at 298 K.
Use the result from Equation (4.25) for the dependence of the
energy levels on a and on the quantum numbers itâ€, try. and at. a. What is the value of the "reduced quantum number"
a=. hf Â«in; +113 for T = 298 K? b. What is the energy separation between the levels a and
a + l? (Hint: Subtract 15'â€œ+1 from El, More plugging in
numbers.) c. Calculate the ratio (l9nr+l â€” EÂ¢)/kT and use your result to conclude whether a classical or quantum mechanical
description is appropriate for the particle. [6] Superposition of eigenfunctions (20 $1
a. free particles. Please prove your answer by algebra. [$44 Is the superposition wave function for the free particle
it) = A.eâ€œ~"â€˜3"'*3â€â€˜3â€ + A_eâ€œâ€˜"3â€â€™Â£;"â€â€˜ an eigenfunction of the
(unintentum operator? [5 it an eigenfunction of the total energy
5:} n 1"? Explain your result. (b)"PIB. Please prove your answer by algebra. P4.12 Is the superposition wave function
:14 x) = Vâ€™fï¬‚sinm'rrx/a) + sin(mnx/a)] an eigenfunction of
the total energy operator for the particle in the box? "" B. Advanced Toplcs (Other advanced textbooks, handouts. lecture notes)
â€œa (None) pendent Study D Modern Applications at Reseach Frontiers [7] Quantum sguare (259$) â€˜
This is the STM image for Fe atoms on a Cu(111) surface, obtained ï¬rst by Dr. Eigler and his group at IBM Almaden Research Center in 1992. and is called a â€œquantum square". Let's model the â€œquantum
squareâ€ as a particle in a 2D box. g 3 (a) Denote the length of the sides ofthe square box by g, (the longer side with 11 Fe atoms) and t, (the
shorter side with 11 Fe atoms) respectiveiy. and the effective mass of the electron by mâ€˜. Please solve the
eigenfunctions and eigenvalues for the quantum squareâ€™s Hamiltonian. If you use the "separation of variablesâ€
theorem. please show that this theorem is applicable to your quantum system. (b) What are the :1K and n, quantum numbers of the state imaged below? (Hint: this is an image of Mâ€œ) (c) Please ï¬nd or estimate Lg, L,. and the effective mass of the electron m" from the 1993 Science paper on
"quantum corrals" (Science 262. 218 1993) dBased on our results In a c what zs the ene y of the imaged state in eV ? E. Extra Credit (None) 1 Problem Set #5 (Chem 113A W'OT, due Thu. 031507 at 11:05am. 100m) Name: Xia nab mu, ( ï¬gâ€, Forming study groups is pennlssible. but you must construct your solutions independently. By writing down my name. i
conï¬rm that I strictly obey the academic ethic code when doing this problem set. Please write down the names of
everyone who you worked with on this problem set under your name. (i) Seven questions, one for each day. As a â€œpunishmentâ€ to the classâ€™ impressive performance, no extra credit
question this time. (ii) Please write out algebraic details and arguments. If you use math formulas or literature values. please cite
your source(s). ,t (iii) Please include these few pages as the cover sheet for your solutions. (iv) if you have difficultiesiquestions. please ï¬nd resources and assistance ASAP. For examples. TA ofï¬ce
hours and smallgroup study sessions. (v) Academic ethics need to be strictly obeyed. No exceptions! Please refer to the syllabus. A. Basic Material (Textbook) [1] Preview #14 (due 02i09i07 Fri.)
[2] Preview #15 (due 02i12107 Mon.)
[3] Preview #16 (due 021410? Wed.) 4 PIB A ll ion : on u ated itbond solvated electro a d uantum tunnelin 25 ts Comment I have heard: â€œLearning science is like eating dark chocolateâ€”bitter at the beginning and sweet at
the endâ€œ. We haVe gone far and deep in this course; letâ€˜s celebrate our accomplishments by seeing how these
principles apply to reallife research. The following are applications of â€œparticle in a box" to modern chemistry. (If you still feel very bitter. please find resources and assistance ASAP. We are here for you) (a) The â€œparticle in a boxâ€œ model can be applied to calculate the energy structure and transitions in rtâ€”electron
conjugated molecules. This simple model is called the â€œfree electron modelâ€. The stmcture of Bcarotene is
shown below. (i) Please estimate the length of the 10 box using 138 and 157pm for C=C and 00 bonds (ii) For
HOMO. n=? (iii) For LU M0. n=? (iv) Please calculate the absorption wavelength (in units of nm). (v) what is the color of carotene ? (b Solvated electrons, application of â€œparticle in 8 SD boxâ€œ. :When metallic sodium is dissolved in liquid sodium chloride,
. electrons are released into the liquid. These dissolved elec
' trons absorb light with a wavelength near 800 nm. Suppose
live treat the positive ions surrounding an electron very
 crudely as deï¬ning a threedimensional cubic box of edge L,
and we assume that the absorbed light excites the electron
' from its ground state to the ï¬rst excited state. Calculate the
? edge length L in this simple model. (c) Quantum tunneling. (Hint: Prof. Lin always modiï¬es Example Problem to make sure students can not just
copy the answers down. Why didn't he modify this question?) EXAMPLE PROBLEM 5.1 As was found for the finite depth well, the wave function amplitude decays in the barrier according to aidx) = Acxp[â€”. i2m{V0 â€” Eli/ii2 x]. This result will be
used to calculate the sensitivity of the scanning tunneling microscope. Assume that the tunneling current through a barrier of width 0 is proportional to A 2exp[â€”2. )â€˜2m(Vu â€” Â£3232 a]. a. If VtJ â€” E is 4.50 tell, how much larger would the current be for a banier
width of 0.20 run than for 0.30 nm? '1 b. A friend suggests to you that a proton tunneling microscope would be
equally effective as an electron tunneling microscope. For a 0.20nm barrier width, by what factor is the tunneling current changed if protons are used
instead of electrons? B. Advanced Topics (Other advanced textbooks. handouts, lecture notes) 5 PlBi D: zer oint one and Uncertain Princi Is 20 There exist proposals and books for extracting the zeropoint energy (ZPE) from such quantum systems as
PlBâ€”â€˜iD. Are they science or science ï¬ction (no need to answer)? (3) Please calculate Axfor the ground state of FIB1D quantum system with box length i. and particle mass m.
(b) Then please estimate the ZPE by using the uncertainty principle AxAp 2 NZ. (Hint: use the exact Ax that
you calculated from (a) and AxAp 2hi2 to obtain 4H5 2 G. Since ground state is an eigenstate of H, measuring
energy on this state will give ZPE with 100% probability. and thus <H> == ZPE. Consequently. C can serve as
an estimate of the ZPE originated from the Uncertainty Principle) (c) imagine you serve as a proposal reviewer for the National Science Foundation (NSF). Would you
recommend the NSF to ï¬nancially support these research projects based on their scientiï¬c validity? (Hint:
compare the ZPE you estimate in (b) based on the uncertainty principle with the exact ZPE) 6 Stern erl ch ex riments an ition Princi le 25 ts
This is the StemGeriach experiment #3 we discussed in lectures.
(a) Please change the second 86 device from 36, to SG, and then predict the outcome (including probability) after the third 86 device. Please clearly show your calculations. Note: 862 means StemGerlach
device measuring 32. (Hint: +Sz> = C1I+Sy> + CalSp. where C1=02=1isqrt(2)) (b) Please change the first 56 device from $6, to SG, and then predict the outcome (including probability)
after the third 86 device. Please clearly show your calculations. (c)The following setup is the Wigner device we discussed in lecture: two StemGeriach devices. 8G2 and 86x,
connect sequentially. Note that the detector is only installed after SGx. After a Ag atom passes 86:. a well
devised magnetic ï¬eld can refocus its trajectory. Assume a single Ag atom in the eigenstate of +Sx> leaves the oven and enters 862, where [+89 denotes the eigenstate of 8,, with eigenvalue +hIâ€™2. What will be the
states and probability detected by the detector if there is no observer (socalled "Wigner's friend") present?
Please clearly show your calculations at each time step. (d) Same as (0), but assume the observer (â€œWignerâ€™s friend") is present immediately after $62 to observe the
single Ag atom's trajectory? Please clearly show your calculations at each time step. (e) Continued from (d). What if "Wignerâ€™s friend" is present but unconscious or totally drunken (say, due to a dozen cans of beer)? Please clearly show your calculations at each time step.
u mu. un. uuuwulgm cqualtull tUl llllhâ€˜KlUUlCIIl SII'ICB [1'18 atom IHICTaCIS Miners {two )Ã©fâ€˜x x
z! C. Independent Study A )1
(None) D. Modern Applications 8. Research Frontiers u 0 uantum corral Hand nut #3: Science 282
This is the STM image for Fe atoms on a
Cu(111) surface, obtained ï¬rst by Dr. Eigler
and his group at IBM Almaden Research
Center in 1992. and is called a "quantum
corralâ€œ. Let's model the â€quantum corralâ€ as a
particle in a circular box. The details of
â€œquantum corrals" can be found in Handout #3:
Science 262, 218 (1993). (a) For two~dimensional quantum systems
with angular symmetry, polar coordinate
system is a good choice: 1: = r c050, y = r sine. Please show by algebra
that alraxz + aha} = aziar2 + (Ur) aiar+ (lirz) 62:69 [hint d f(r,e)ldx = d f(r,e)idr'(driâ€˜dx) + d f(r,e)lde*(deldx)]. (b) Please derive the corresponding Hamiltonian, the timeindependent Schrodinger equation. and the Born (boundary) conditions in the polar coordinate system (no need to solve yet). (0) Please rewrite the TISE you derived In (b) In terms of dimensionless variables ofor radius and 52 for energy, where the dimensionless variables are deï¬ned as: c: rte and s = 2ma2El'h2. where a is the radius of the circular box. (d) Using the â€œseparation of variables" method in solving differential equations, we can "divide and conquerâ€. Assume the eigenfunctions of the Hamiltonian have the form Raï¬) = R(o )603. Please derive the two differential equations governing R(o ) and 6(3), respectively. (e) The differential equation and the boundary (Born) condition governing 6(6) is exactly the same as that In
"particle on a ring" (PS#5) and you have it solved already. Now letâ€˜s focus on solving R(o). Denote F as the "separation of variable" constant. Show that the differential equation governing R(o) can be rewritten as arcsâ€”â€˜4 soâ€œ; ï¬azmaï¬+mmaï¬+w43m=o
where ,8= 05, t=0,l,2,. .. . (0 Show thatRUS) = O at the. This is the boundary (Born) condition for R(o).
(g) The radial equation in (d) is the Bessel equation whose solutions are called Bessel functions MB). Please identify how the allowed values of the energy E are related to the nth zero crossing an; ofJKï¬).
{To be continued in PS#6 â€” you may want to save a copy of your solutions to [7]) 11 m mullIIIIIIIII
Iglllllllllll
lqï¬ï¬‚gï¬‚llllllll
uncannggggs!!!
aamnnngngsnnnn
Ilamumzanï¬naï¬.Â» 02 . ._., __ _ .534 IIIE'Aï¬lllllll
a 2 4 6â€˜ a no .12 a E. Extra Credit (None) Question Number 7 ...
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 Winter '07
 Lin
 Quantum Chemistry

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