Name:

Student Number:

PHY294 Quantum and Thermal Physics

University of Toronto
Faculty of Applied Science and Engineering

April 28, 2023

Duration: 150min
Number of pages: 22
Question Maximum Marks
1 20
2 20
3 10
4 25
5 25
6 25
7 25
Total 150

Answer all questions on the question paper in the space provided.

Write legibly with a pen or pencil.
Do not separate pages
Exam Type: B, Calculator Type: 2
No aids are allowed except for a non-programable and non-communicating calculator.
Questions 1-4 on pages 2-10 relate to the Quantum Physics half of the course.
Questions 5-7 on pages 11-16 relate to the Thermal Physics half of the course.
Pages 17 and 18 may be used if you run out of space for certain questions. If these are used
you must indicate that you are continuing your answer somewhere else in the space left for
each question.
Formula sheets for the Quantum and Thermal portions of the course can be found on pages 19-
22.

1
 1.(20 pts). Brief explanations.
a) (5 pts) What is the selection rule for the absorption of light for electronic transitions
(exciting electrons to upper electronic levels) for multi-electron atoms with respect to
symmetry and spin?

Spin =
DS =
0
(no change in overall
spin)
multiplici
(25 + 1) can't change
Spin

34mYmdt FP what we need

m
= is

(odd integrates to 0) so allowe

So ↑nuYm is even

summate in functions
change of wave .

involve
transition
a

info to size a

because need some dipe moment

This is had

that chunger electron distributions

FME -O can .

b) (5pts) Explain the Pauli Exclusion Principle and the need for antisymmetric
wavefunctions to describe multielectron atoms or molecules.
2 elections
soli-Exclusi Principle
↑ states that no

state Lies contain the

can occupy
the same
grantin
4
numbers n. l m . wi)
quation
.

same

ware fructions ensure

probbing
The antisymanz
state
of two elections being in see
grante
to 0 (forbidden)-
sums up

2
 c) (5 pts) Describe hydrogen bonding in water specifically discussing the structure of
water (valence orbital hybridization) and number of hydrogen bonds in ice and liquid
water.
and will
H bonds ul O LO has hisher EN

attract to H on other H20s)

go
lesse 0
densit >
-
more - localization on

OH H Ice :
Y H bonds per water

Sp hybridization Liquid : GoY H bows

per
water

109 50 . bool angles

d) (5pts) Franck-Condon Factors determine the transition probability for the absorption
of light involving vibrational levels between different electronic states (eg. So and Si).
Write down the equation for the transition probability including Franck-Condon factors.
Briefly explain how the nuclear probability distribution weights the transition probability
for the absorption of light.

3
 2. (20 pts)
a) (5 pts) Using the molecular orbital diagram below (LCAO-MO) and the Pauli
Exclusion Principle, assign electron configurations from valence orbitals to molecular
orbitals for O2.
- 6 value elections each

↑ L↑
⑭
—TTi—
144
2p
oaa
O
D-
□□
'—4746
↑ L
/

3-
⑪
↑ ↓ ↑t
I
2s

⑪
t

Q
C2S

↑Qb
↑□
Is
b Th
>-a
is

El a
↑ □
b) (5 pt) What is the bond order of O2 and O2*? Which species is paramagnetic?

Do not consider
Is in bond order (not valence)
02
(8-4)
For =
2
antibonding) 1
=

C boul
=
- #
Bo =

*
elector from # P
For Oft reade
one

Bo =
z(8
-

3) =

E 4

paramage I has pain

love
Ot is a
 c) (5pts) The heteronuclear diatomic molecule NO is an important cardiovascular
molecule that increases blood flow and is involved in cell signaling. Repeat the above
assignment of electron configurations for the molecule NO. Redraw below the above
molecular orbital energy level diagram (problem 2a), n=2 valence shell suffices. Show
explicitly the relative energy ordering for valence orbitals for N relative to O in terms of
contributions to the molecular orbitals.

C 42p
-

&
1 I
+
In I2p

I
enerny
S
2p It I 2

En P

It 52s
*

↑ ↓ ↑ ↓ Is
25
Itas
-

D
N

5
↳ valesce
Valence

d) (5 pts) Which molecules have IR active modes for O2, 02'^ and NO? Brief explanation.

5
 3. (10 pts)
a) (5 pts) Referring to the figure below for double stranded DNA, state the valence
orbital hybridization and geometry (bond angles) around the C atom and N atom
involved in the G=C hydrogen bonding. The central atoms in guestion are indicated by
arrows in the figure below.

md

5' end 3' end

N-H««****’*O
h

h -n /” 1^0
:h
1
O

1
H

%
A,
b*-„
H \
I H
/N—H«
"Q.

—H-h

OH
T^
OPOj-
H O

3' end 5' end

5' end
H
-
C- 10 H -
N =

& >
N 3
>
SP
hybridization
Sp hybridization
10950
1200 boad angle
bond ans 6
 b) (5 pts) Levinthal’s paradox refers to the enormous number of nuclear configurations
associated with protein structure and search process to spontaneously find the active
biological structure. The protein folding problem involves the collapse of a hydrophobic
core to guide protein structure. DNA has even more nuclear degrees of freedom yet
forms a double helix with virtually no error based on complementary nucleotide base
sequences. It is so robust that it is possible to “program” DNA by base sequence to
have the double helix twist and turn into specific shapes called DNA origami. Note, the
interior of DNA is not completely hydrophobic. Discuss how DNA finds its double helix
structure using the funnel model and identify the various forces that define the gradient
directing the system to the double helix structure. (List all the forces involved in forming
the DNA double helix.)

~ dofs of DNA aminoaids

are not independent

I &etmus
ener-
a
7 -
unfold

>
- filded
&
-
....

ruh E

structs and hidose

Chipem poteh
,
secon
,

all work to minimize protest

bund network (collapse)
to low E biological
folding it a

volume by
active state

Continued next 7
page
 at
Internalow forces play:

I bonds (exist blu bases)

phosphate)
dipple (water
and closed
-

in

-
dipole-induced dipole ( frn,thrtk inastone)
- Van der Und (evemute)
intermodular fors at play
Also
~ init
bunds

=
covalect brads (sulfer bridge)
 U
4. (25 pts)
a) (5pts) Write down the Schroedinger equation for the Harmonic Oscillator.

[+kx2] Y EY
=

H
b) (5pts) What are the boundary conditions to solve this differential equation.

As - > I He unfunction 4- 0

c) (5pts) The wavefunction solutions involve a series solution, i.e.,

ihn (x) = (^2.), „ = 0,l,2,3,... with E = (n + |)hv, where:
■^0 (y') 1 . n A n f ^12
H,{y} = 2y with y = px and p
H2 (2/) ^A.y‘^-‘2
H3 {y} 81/ - 127/.
Using the above functions, write the mathematical description of the probability
distribution for the zero point energy solution.

is o
Zero point
Esolute
at

↑o(x) =
Ne Ho(Bx)
1 > Ho(PX) = 1
Holu)
-

=> Note that =

B
Then 40(x) =
No

distribution
is
/Yo(x)/2
Probabin -
B2x2
% cores from
/40(x)
<
ze S
So
-

P(x)
=
32x2
A
1
-
=

S
=
ce

this watches the were functio shape

8
 0 1. 2 3
= ,
n ,

-
d) (5pts) Draw the probability distributions for the first 4 vibrational levels in the potential
below. Clearly show the region related to the tunneling probability for a given reduced
mass (shade the relevant area).
t he

↳
in of
E (a z)hv
Energy.
= +

amplitude outside of turning

points
&
Meet -
£ Y

-
Un --- - E
-

-
,

1
&
-

2
-
-

&
-
#
- --
/
-
an
I I
- -
- -

- I

-
-
S- - - -

X
-A 0 +>A

e) (5pts) Derive an expression to determine the overall tunneling probability for a given
reduced mass p. and force constant k. (Hint: Derive an expression for the classical
turning points where the energy is all potential energy.) You do not have to evaluate the
integrals, just show the proper limits.

Want 1412 = U
B2x2 2

Hn2(Px) 1
-

=
x
Then Ce
xit e
as
x

ensegehenfor
=

↓
9 both sides
the 2 is for tunnelin on
4. e) cont.

10
5. (25 pts)
Answer the following questions qualitatively. (No long-winded expressions and
derivations!)
a) (7 pts) Why don’t we have to take into account the structure of the nucleus when
considering the partition function (or, in general, the thermodynamics) at room
temperature of, say, a hydrogen gas? How about the (supposed) string-like structure of
the electrons, of the quarks inside the proton, etc.?

b) (4 pts) For a monatomic ideal gas of atoms of mass m, of number density n = N/V,
at what temperature do you expect the Cy = |kN law {Cy is the constant-volume heat
capacity) to break down? Answer the question parametrically, i.e. find the dependence
of Tc on n, m, and on any fundamental constants that might be involved, neglecting
numerical factors.

11
c) (8 pts) Does thermodynamic stability require that Cv be positive or negative? How
about f—) , a quantity proportional to the “bulk modulus” (a measure of the material’s

stiffness)? Explain qualitatively why.

d) (6 pts) Much of the material of this class used the “Einstein solid,” a collection of N
simple harmonic oscillators of frequency co, as one of the toy models of statistical
mechanics. One reason for this system’s domination of the course is because it is fairly
easy to study. Do you think the study of the thermodynamics of the Einstein solid is
relevant for real physical systems? How about the study of several Einstein solids (say
with different frequencies) in thermal equilibrium? Enumerate as many examples as you
can possibly think of (only a qualitative discussion of their relevance is needed!).

12
6. (25 pts)
Consider a two-dimensional gas of point-like particles of mass m at temperature T
(recall that a computer simulation of a two-dimensional gas of billiard balls, shown in the
first and last thermal physics classes, was used to motivate much of the material in this
course!). Here, you shall consider any one particle of the gas as the "system" coupled to
the “thermal reservoir” of the rest of the particles of the gas.
a) (20 pts) Use the Boltzmann distribution to find the probability density P(v), defined
such that P(y)dv is the probability that the particle’s speed is in the infinitesimal interval
(y, V. + dv). What is the most likely speed of the particle? Normalize the probability
distribution and use it to compute the average kinetic energy of the particle. Did you
find an answer you expect? Explain. (Various integrals you can use are given in the
formula sheet.)

13
b) (5 pts) Apart from computer simulations (a numerical “experiment”), do you know of
ways to measure the speed distributions of particles in a gas (in three dimensions) in a
real experiment?

14
7. (25 pts)
Consider an Einstein solid of N oscillators of frequency a>. Recall that we take (setting
the “zero-point” energy to zero) the energy levels of a single oscillator to equal hco times
the number of quanta excited. We studied the Einstein solid using the canonical
distribution and found the partition function of a single oscillator, using /3 =
\Ne also studied the Einstein solid using the microcanonical distribution, where we
determined its multiplicity function n(yv, q) (q is the total number of quanta excited in the
entire solid). When N and q are both large, in the q » N limit, the multiplicity function
was found to be Q.high(.Q-^} - (^) •

a) (12 pts) Use the single-oscillator partition function Z-^ to find the entropy of the gas as
a function of the temperature, S = S(T,N). The expression you find may look daunting at
first, but don’t despair: in what follows, it is sufficient to consider the expression for the
entropy only in the high-temperature limit. Thus, you may want to simplify S assuming
kT » ho}.

15
b) (7 pts) Now use the multiplicity function Q.high to find the entropy as a function of the
energy, i.e. SQE.N), in the q » N limit. Use the statistical definition of the temperature to
express the entropy as a function of T in this limit.

c) (6 pts) Compare the result of part b. with the expression obtained from the partition
function (part a. above). Are you surprised? Do you have a comment on the result? Do
you find one calculation easier than the other?

16
Additional space for answers. If using this space clearly indicate which question your
work corresponds to.

17
Additional space for answers. If using this space clearly indicate which question your
work corresponds to.

18
 Equations for Quantum Mechanics Part Comment
E = ftv_________________ Photon energy__________________________
4= Er = 13.6 eV Energy of hydrogen (Z=l) and Hydrogen like
£’n = - 8/12^2
atom with atomic number Z______________
Einstein Photoemission relation
ftv = (1> + -rngV^^
___________ AE = E/^ — Et = hv___________ Photon transitions between quantized levels
(x) = Wx}, n = 0,1,2X7 QM Harmonic Oscillator wave functions
E = % mv^________________________________ Kinetic energy___________________________
U = 72 kx^ Potential energy for harmonic oscillator
h Uncertainty Principle in momentum/position
> —
________________ ___________________
______ F(v) = (SnvVc^) hv/(e*^'''^'''- 1) Blackbody emission/spectral density
U = -ZeffkeVf where Zeff —>Z as r ->0 and IPA potential, extrapolation of limits in Zeff
Zeff-» 1 as r—>co from Gauss's law

E = (n+%)hv; n=0, 1, 2, 3... v = -1^ Quantum Harmonic Oscillator Energies,

resonant frequency, and reduced mass
+ irin
ay Three Dimensional Schroedinger equation
for a single particle of mass M.
h Uncertainty Relation for time/energy
AEAt > —
f = ZeV4n£or2 = keVr^; U = -ZkeVr Coulomb force for charge Z protons and 1 e;
Coulomb potential energy for Z protonsand 1
electron_________________________________
h De Broglie relation
_________________ mv p
Pmn = {IVmgVndXe}{IVm(v)Vn(v')dTv} Molecular Electronic Transition Probability
weighted by Franck Condon Factors
Pmn = JxHnPVnidT; Transition Probability for absorption of light.

-(hVSn^mldVdx^ (V ) = E\|/; U(x) =0; 0 < x < L; Schroedinger eq. for ID Box
U(x) = oo for X < 0 or X > L__________________
\|/ = (2/L)^^^sin(nn/L)x; E = n^hVSmL^________ Solutions to ID Particle in the Box
U = -ZkeVr; U = +keVr____________________ Attractive potential of nucleus; repulsive e-e
£^E = ; m = 0, 1 ..+1 Zeeman (mag. field B) effect re: Orbital
angular momentum______________________
B = :±P.b B Zeeman effect (B) re: spin magnetic moment
________
L = \/l(l f- 1)A . S = + 1)A Quantized orbital angular; spin momentum
/ = 0, 1, 2, 3...; ms = ± %; Lz = m ft and Sz - ms ft

Bond order = (number of bonding e - Using Pauli Exclusion Principle to determine

Antibonding e)/2 number of bonds from MO e configurations

19
N^iiied Consents Plahclc’srGoii^ahtsL^ ft = 6.b3- x
.Atomic in^i.urii t: lu:-4^tt^'’Catdml = 4.1^1 s? ir’^ ev-4i
= 1.66 X lO'^^kg.
=:931:-5Me\7^'' = fi:58,:X
Avdgadro'sediistarit:; V* =.K02 XilO^partKlesftnold,. Rydfe^xc^staint:
=44Q:X
Bohr magnetoh; J^dbereenergy: = hcR=:mJ^^l^^
= >5:79x40^^ey/T """ =...l^:6.eV
•=:.3.27'x;iO'?^^i/T(^orA-.ni?> c ^<3^^ 10^ m/s.
Speed of lighh,
Bphr.r^ius:.
^35^9 xdO'^'m;
Bdltzmann’s Gonsfant:. :fta - SiSl X lO-^eSiTK ljs^fiiK:dmKinaiiOns
''' = .i:38:>C'.i6-®'l/K- hc ~ i^:eV<nm. =
JCddidfhbfe^eGdnstaiit: ■k. l/(4tt^)
= =137 MeV

E^trdnGdmptdn k^=:Hh>n^ . 1.44feV>nni = i.44.MeVvfhr

wavelength: =r:'2a3 xll)"‘-nv (luj Lgi'am
EfeeWbiivoltf leV:= L6D :x;:10'’''*3; = 6:0232.eV-at, room lemperaiure (^3-K)
Efemehta^ehatge:; ?'r= l-dO^XOlQ-^^G
Fine'-strttcjtee
Gohstanl: :^:X36"x.]:(P fe
.Goliveisidh! Factors
Gasdon^hi:: 2?=.g3i;3^(hidte>K)
= 6:0821, liter ‘jatm/tmole \K1 Area; •ibaia. 1-6”—

Gravitational constat:, G = .6:67-X^ip’-”n-m^kg?^ .^?Tsy; i cail

MasSpf:eiettxpfl: m,. A 5,^ x.lO''V iey .= 1.66 X tdr’Aj

= 3:11 X 16-^1 kg. Length: 1 A = i angstrooi
:= 6oiiMeV/<?
Mass of pratQQ; Z7rp,= .l 607:u :
lft =^ 30.48 din-
= "1.673 X-16^-fcg
=-338i3MeyA? 1th = 2.Sif cm
J rai’;= 16Q3m
Ma3s:df;neutrdh; w„ =1.003%
= 1,675. X^lp"~-kg Mass: llb(niass} = 6:454Lg.
-=-93iy:M^/^ l MeV/^' = X lp’^u
Naelear magiietdn; .= ■1.783 X- itr^' kg
= ,^i5xib-^v/t 1 u: = -^in{'3e;atom)
= :5,65 X10"^’3/T
Perrneability xw-W^. =. 931:5 .MeV/c^
^•fspsice: ■ = 1.26.XiiO’^W^
=1.66,X10^kg
Perrniniwtjr
” lO"*-'^ 1 MdY/c 5L34'-X .lO-^^^lcg ':iii/s
•ofspace- Moihehtiun;

20
 Periodic Table: Electronegativities

I >
Pauling scale
rTTFf< 3.5 ' 'Il
>24; fA
| - V°^g ( PyljPap
ff2.orn-4~nl sr-fCK-ssi/rs

iS=n Br
«■»
—I...-- -.1 c .^.. lEi-.«.. r-i-------------

Q;9
n d.Q
■PM “ .22-®%d-ir
1. 6' r IgB^ nr
gss ■ W1'^ BS
iff
-fefta.

t -2
WsW"'"'
3 ■4 $ S ?■ 8-
J
9 la 11 12 13 14 IS 16 1?

Periodic table of the elements

O Alkali metals. 113. Halogens.

I O Alkaline-earth' mietals Ndblie gases

s.
o
18
S Transition rnetals O) Bare-earth elernerits f21,39,57-71)
and lanthanoid elements ^-71 onl^O 2.
1 0 Other meteds 13 14 15 16 17 He
2

BP «^g^|i6
g] Other no.nmetals Acfrioid elemerite
2
IB ““"1 Ne

3
B 6 12
13 g|«B4
aa Ar

H Bl a
3 5 7 .8 9 .10 11
P®P?S|36

■■
iZSgiTE
,4 ■1^
s^lblSS : V g^i Kr

5
11 iHasa®^
a agiiaE^!
s gat In ,:L:^
g^S
^24 i51i":-i';
Xie

S: p
MO

ii S’ (HjBfi
88

■B
6 ;ps. Rn
OTili
1^
■fe
113 >
7 ' —- :
i^VrNh l.-H Og

lanthanoid series 6
S9T'"^
KS Lalifej Dy!
<3^
Wq

^|;;.|u'npr^^c.nfB.c.rcfi.
!96'i;’5;3
actinoid series; 7

■Numberirig system adispted by. the Inierfiation^ Union of Pure and Applied Gherriisiry (lOPAC). © Ericycldpaedia Britannica, Inc.

21
The ideal gas law is pV = NkT. The energy of a single-atomic classical ideal gas of N atoms is
U = ^NkT.
2i
The work done by the gas in a quasistatic process along some curve p(V) in the p — V
v-i.
plane is W = J p(V)dV. The thermal de Broglie wavelength of a particle of mass m at temperature
Vi
T is Xth. between the thermal de Broglie wavelength and the typical distance
between particles in the gas (as determined by the number density of the gas) determines, roughly,
under what conditions a gas can be considered classical and obeying the ideal gas law. The energy
levels of an oscillator, ignoring the zero-point energy, are liwn, where n > 0 is the (integer) number
of quanta. The first law of TD expresses energy conservation: the energy of a system of fixed
number of particles can change because of the heat transfer and work performed.

The microcanonical distribution (for an (£?, V, 7V)-system) states that all accessible microstates are
equally likely. The TD potential is the entropy, S = k In £7 (E, V, N), where Ci, is the multiplicity
function. The TD identity dS = ^dE + ^dV - ^dN can be used to determine the temperature,
pressure and chemical potential as partial derivatives of S.

The canonical distribution (for a (T, V, N) system), upon denoting = fcT’ is; P('microstate') =
, where Z is the Boltzmann partition function Z — E Q ^Emicroatate Tlie
microstates
TD potential is the free energy F = E — TS. The partition function determines F: F —
— ^\QgZ{T,V,N). The average energy of a system is E = — -^\nZ. The TD identity is dF =
-SdT - pdV P ndN.

Nuclear energy excitations are measured in eV and are typically of order GeV, or lO^eV, where
leV ~ 10“^^J. The ‘-fundamental string” (of the putative “theory of everything”) presumably has
a characteristic scale of excitations lO^^GeV. The Boltzmann constant is k ~

Some useful mathematical expressions are;

= -, lnx“ = olnx, Ine = 1, = x, • dx

^a(x)^
cte ’
dx ’ ax
function e-^ 0
dx x^ dx ■“ “ ''

as X —> 0 and is positive for x > 0 (also ~d^-|x-^o = 0, for all n > 0). As a: —> 0, ~ 1 — x -H

Various Gaussian integrals are as follows:

CO oo oo oo
VTT , J dx 'X' 1
J dx e —ax"^ z r>
2a2
J dx X e
2a’
y dx x.2‘
4a 5
e
2a2
0 0 0 0

22