BLACKBODY RADIATION

blackbody opening c xv
=
=
2.998x108 m/s

3.
detector wavelength X

frequency v

classical
in theory
- - -

"Rayleigh- Jeans Law":

↑radiation
heat
Pr(T) 2kxT2
-

23
density of radiation
(infinite)
in Quantum Chemistry ultraviolet increasing density, of
radiation w/ increase
8th ~3 catastrophe
·Pr(T) =
intemp X
non verbation

assumption electparticles is quantized

E
=nhv;ne

Max Planck, 1900 ↑ classical law

L
Match exp'twhen
h 6.626x10- 34J.S
= X

Planck's constant
Ts Tz T

Intensity

~fall -

Photoelectric Effect >MASS

KE nv
=
-
hv
/

light source KE 2 Mv2 =

- nv I

↳ pe velocity
-

Been
UV light P =

HW (work function) v c
=

ejected CLASSICAL PREDICTION ACMALCQUANTUM TORT

X
electron X

L L
" -
KE KE 7
11111111/3
metal
not dependenton I!
surface
7 I
intensity, I intensity, I
1886 Hertz:UV light removes

e from metals X
Vo
I
1905Einstein:Aypothesis KE KE
I
(Quantum Theory)

photon have quantized energies I

0
(E nhv) =
freq freq
 R-DBERG FORMULA

yuv
1VIS -IR

LYMAN BALMER PASCHEN

< 3
Wavelength, x)
W
i =

c 2
=

RH 109
=
737.3 an

Rydberg constant

kH)ir
i n>I

in)
Lyman
=

3
-

n+ R

Rx( i)
i Balmer nxz
=

paschen
Rx(
v n>3
iz)
=

↳ Rexideasthis is a come from?

R+(+- )
v = man, so
n z, n,e R

↳> Rydberg Formula

↳ quantized nos.

BOHR-HYDROGEN MODEL (BOHR RADIUS)

Angular us Linear Motion

I
I < 7 M

resagainst
L other
Mp
I mass

l
W < I v
7
angular velocity linear velocity
> =
c
b
-
X
m2 V I
moment of inertia linear momentum

T >
-

I
Kinetic energy
I mv2
=

freq. of rot.
y
v rw
=
2πrr, circumference
=

p mv
l 5w mur
=
=

e
I
Mv2 perfectcircular motion
=
Clinear) T =
= in

Cangular) T
=

=Iw2 I
=
 -

+ 7 Wave-Particle Duality
CO4lOmb
-
centrifugal Einstein, 1906:light is both a particle
force force
↳
not actual and a wave
force
DeBroglie, 1924:Matter too!
(+ e)(- e) MeV
(for part, rot) h
4
-

x
4K Ei r
=
=

two unk:V and r P mL, velocity

assumption:I is quantized (Bohr, 1911, ↳momentum
if big, it is very small
~> reduced planck's m is

l nh =0,t X (wave behavior not evident)

3
=

constant n as

4 = in integer if m small, yo
is

27 becomes measureable.

l MeVr
·

meUr nh
n() "( )
=
=°

air nx
=

v nh
=

Mer mur=nh =e nh =

21L
-

↳t
(here
e2
quantization
me
Bour
X
=

condition
4r2
t
men
=
e2
-
e
- n
·I
r 3
-
Heisenberg uncertainty principle
411E,r2
-

emer=44Ench smaller wavelength, smaller DX

r 4πEont2 uncertainty, up uncertainty.

bigger,
=

eme p: momentump
- b due higher
=

to
r 5.29 x 10
=
m freq.
v =

52.9Pm
-

3x1p =
r 0.5291(n 1)
=
=

↳Bour radius, 90 Bour model fails to predict

*100pm 1
=
=100m Ax at the same instance
as
p (or an approx.)

BOHR MODEL -
ENERGY

1 V potential energy
~

(coulomb potential
E =
+

CLASSICAL WAVE EQN

e
MV
I (x,t) displacement.
-
for as wave

4 i9 classical wave equ ↳(space, times

Inganong dili negative and eq'n sq 02u(x,t) I 22u(X,t)
=

coulomb force ganina?) &x 2

V2 0+2
↳
negative
Basin gynd and coulomb pot?assume u(x,t) X(x) +(t)
=

via separation of variables)

[Wala nako ginuman=(]
 22(X(x)T (x)) ↓&(X(x)T(t)) & any X,
= ↑

BsIn
X(x)
nx.x)
2
0x2 12 2+ =

(X(x))d+
=(t)d2X(x) =
(t)
dxZ dt 2 Time,
For
d2T(t)
x Gcs(nπvt) bsin()
I
·
T(x) =
+

-
2
v 2T (t) dt l
!same argument, diff coeff!

I,z
=
It is possible to fix via phase factor

Ews(* 4)
=

-
-
vt +

↳ diff phase factor

q4x(x) =
53X(X)
constant
related to ratio
ofC and D

d(T(t) -
3vT(t)
SO,

n(x,t) A
cos,*rt+ p/sin(x)
=

d+2
=

Ancos(*r+bn) sin(n
Whenever the second der of a fin equals n(x,t) =

a negative constant squared times itself, ↓another

speed component
the solution to those will be sines acosines ↳ smaller & (length),

X(x) Acos
=

((3x) + Bsin (Bx) can be decomposed into faster flipping wave

of

T(t) (cos(But) Dsin (But) called modes

=

+ normal
[Un(x,t)}
we are standing waves
VIBRATING STRING ↳ moves in time, but notspace!!

I I
Schrodinger tan:Deriving the spatial term

(a postulate; assumed to be true l

⑳ - - -
-

B
into
- - - -

n(x,t) 4(x)cos(wt)
= ->
anyth
-

0x2
spatial amplitude

t
0 l =

boundary condition's

cos(wt) (x)
=T(x)(f) wcos(w)
y(0.t) true for all t
3
=
0 -

dX2
n(r,t) 0
=

x (0) 0
=

Acos(B.0)
=
+ Bsin (B.0) aix) 24(x) +
o
=

w
A.1 B. O ↳ (πr)2 4422442
- =

X(0) A nocosine term!

0
(2x)2 2x2 32
=
=

X(l) 0 Bsin(l) true &"Nex),

$124(X)
=
=
=
0 A
for all values =

Bl sin (0) ni dX2

=

ni
sin(B1) 0 =

B
=

2quantized!
l
relating &
to E I 2x+ 3 x 4 2x2 + 3//X
not a linear operator

E Pr
=

+V(x)
Total Energy
2m A classical properties are related to linear,

*,
quantum mechanical operators, every
true if indepentof time
p and a conservative sys property has an operator A

↳ momentum

R h =
h h EIGENVALUES G EIGENFUNCONS
=

p aπ Operator (function) constant. (same function)

.
-

.
.

eigenvame equ
from A

442 4 i 2p
2
p2 2m(t -v(x)) 8f(x) w(f(x)) =

eigenvalue of the eigenter

I

42
= =
on thatoperator
-2 h2 42 eigenfunctionof operatory
the

cox) am + Vexs/YxTo
↳
EingYng daw
nawala lagi ang Y(x)
the eigenvalue problem

given o, find the set of f(x) and w

finally from (442/x2) 4(X)?

-h d "Y(x)
V(x)Y(x) EY(x)
=
Schrodinger eqin (factored)
+
dx2
1 v(x))4(x) E4(x)
am =
-
+

ine IndependentSchrodingerare
e

2+
it
-

= v(x)

OPERATORS Situmiltonian operator

does something to an objectthat creates a TTY(x) EY(x)
=

new object.
property we can be
examples operators:every
different measured inclassical property

of(x) g(x)
=

has an operator
Hamiltonian operator
X

q+(x), Sf(x)dX + total energy

H
Tx), -
=
V(X)

2 f(x) )
(f(x)/2 Kinetic energy
P
LINEAR OPERATORS
=-

* de

Potential energy
-[c,f,(X) (efz(x)+ ...) +

c,8f,(X) (20fz(X)+...
=
+
P V(X) =

↳
coeff operator acting on f.(x) Momentum in x direction
8 (cifi(x)) Y,ciofi(x) =

Px -ind =

where
[in K dX
X-position squared
position
&(2x2 3x) 2d(x2) 3)
-
-2
IX
+ = +
X X
=
1 x2
=

dX dX Momentum squared

the
since equality is true, itis al Bx 2
=
= d2
linear operator x2
 I
WA IS A WAVE FUNCTION? PARRUE IN A
BOX
-X

↑(x) wavefunction
14(x)12 4* (x)Y(X)
!Need to specify V(X) for

1
I
w i -

0
x
=

0 x x
if O X l
v(x)
-
->
probability density a otherwise
4(X) outside the box
schrod eqin: and the borders is0

is
↑(X) TY(x) EY(x) =

0 -

(x) v(x)Y(x) EY(X) +

=

-am*P(x)
d24(x)
·

I
=

dX
/Y(X))* 2

t
Tip:If the eain is a second dev. isequals a neg.
results
constant times the same function in

a offines and
combination cosines

-
2ME
0
↑(x) AcOs(kx) = + Bsin(kX) k =

↳
X
Y(x = 0) 0 Y(0) boundary/border
3
0
=
=
->

4*(x)Y(X)
2
14(x) 1 =

P(X,0) 0
=
- >
4(t) 0
=
conditions

Re2(X) +I(X)
-

4*(x) Re(x) -iIm(X) ↑(0) Aws(k0) +

Bsin(k.0) A

ynet
k
= =
=

Y(x) Re(x) +i1m(x)

=
↑(1) Bsin(kl)
= sin(0) ni
kl= =

Born
4
Interpretation: Yn(x) Bsin =

(x) n 1,2,
=
...

4*x)4(X)dX is the probability that Ni

-
12mE n h
I
amE I -
D
the particle is between Xand x tdy. l I en 2π
for smaller dx En = hin n 1,2,
= ...

for larger dy, integrate. Is the Y) is 8m2 ↳quantum number

going on dx.
to
change depending
now. What is B in
Mn(x)=Bain(**x)?
30 dxY* (x)Y(x) =
NORMALIZATION

Incxs/2dx Y(x)4n(x)dX:probability
-
=

The probability density over all of x particle position x+dX

space. 1Y*(x)Y(x)dx 1
=

> NORMA LIZATION Y(x) 0

=
if x = 0 or x > l

Bigger I4(XS12, bigger probability 1 =

1)Bsinx]* [Bsin(ax
No imaginary number so 4*(X)4(X) 14(x) /2 =
1 Br
=

J sinz,*dX
sin(kx)
1 (1-cos(2kX)
=

↳
trig identity

B2g(1-cos)]dx
1
=

= (X- sin) anx18 ( l

E2 (- isin(ane))-10-sin
0

anto
=

B
z 15
=

e
-
=

4x) J
=
sin nit X

B isthe normalization
constant
makes sure thatt he
A isequal to 7
integral *

AVERAGE POSION

to calculate the are position, we use the

operator.
(A x (,dxYY(x)AY(x)
=

for is from Yu(x) E sin (nY),

=

?dxsin(M*]*x Il sin(**]
-

x =

=)xsin)**Y)dX k
A
xs
=

(xsin2((x)dX 0
=
-

COSRRY) -xsin(akX)
2 * s()- xsin(Y)!8]
<x =

(x)
t)e
=

10)
24 I
=

Names
ofsave position
ixx l
=

2 inYn(X)
 for XX2>,

x=
1? If
sin
(*)* esin(n))dy
<X2)
(?*"sin?) x)
=
dx

(xsin" (kx)dx itcos(nkx).213x3-1

=

8k3
sin(2kX)
+
incomplete!
x2 =
YT* (e +

x=
((- ) * -

10+ 07

&n 1,xX2),
(x2)
e)- nz) 0.2832
= =
=

&n x,[X2)a
=

l2
=

VARIANCE
the uncertainty

- variance =tO
STANDARD DEVIASION

5 1,dxY*(a =
-

xxx)-4(x)

<A2y
=
- (A)2
↳
these a aren'talways equal

of
(e) anz))- ()"
e2(
=

)
o
e! sin
=

(0x) =0.181 l

(x) =0.289l

·x l
Lox? OS*
 UV-VIS SPECTRA OF POLYENES

nu

3DE
2

p1 ethylene
> =

1
l

-3D5
ne i3-butudience
P
=
-

11
l
11

3*
-

1
-
nv, 43 =
1,3,5-nexafrie e
e

↳
-

e = Dez
En st hv
=

=
(n2-)

Inn, in-site
X hc
- -

2
DE 2p 1
=
+

Rc= 1.34 Rc -c 1.47 So, for to

=

p=1
pt(m)
=

I I
P Xcakum
↳

using R 1.39
=
A 1.39x100m
=

21 171

l (2p=
-

1) R ! 115 217

3 228 258
R = ⑧MC
-(2p 1R3") 4

3 30
-

↳ 2p+ 1 5
AVERAGE MOMENTM

operator:
P -
= ind
dX
i2 Pp =
=
= h2d2
dx2

(84*(x)AT(x)dx
-As =

↳ value
expectation

<Pc
jdx)singnx)
=

citty)[sin(n))
<p =
z(in) (n) Jedxsin() cos( e
(sin(kx)cos(kx)dx cos2(kX) @k y
=
=

(p)
(ih)(2)( )(ws2,x)18]
=

l
-
osni-
e( I I w32(0))
=it

it
-
(1) what does that mean?

particle is equally likely to

0
<4) =
the go to
the left () or to the right (t)

spraSothesincethenetn(**)ax
(2xx) ;k =
(sin" (kx)dx
sin
is
=

=Chi(-isin(2x)(8)
13
2
242n"i
-
I
exe (4- 3] note!review jud your trig diff
<x h2πn2 integrals!
- trig
=
and

12