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Rigid Rotors — molecular rotation and the universal angular part of all central force
problems – another exactly solved problem. The rotor is free, thus H
b = Tb (V = 0).
b2 , J
* effects of J bz , J bx ± iJ
b± = J by (“raising” and “lowering” or “ladder” operators)
than we are in the actual form of ψJM (θ, φ) and in the method for solving the rigid rotor
Schrödinger Equation.
P
* [Ji , Jj ] = i} k εijk Jk definition of an angular momentum operator
* Jz ψJM = }M ψJM
* J± = Jx ± iJy
The standard problem is for the motion of a mass point constrained to the surface of
a sphere. However, we are really interested in the rotational motion of a rigid diatomic
molecule. Mass point is the same as one end of a rotor (length r0 , mass µ) with bond axis
extending from the coordinate origin at the Center of Mass.
5.61 Fall 2017 Lecture #17 Page 2
M is projection of
J on Z
J
M
θ J
m1 r1 rcm r2 m2 Y
X
at origin, J “precesses” about Z. Why
r0 = r1 + r2 do we say this when there is no
motion in solutions to TISE?
For a molecule, there are two coordinate systems: the body–fixed system denoted by
x, y, z and the laboratory-fixed system denoted by X, Y, Z.
1. E(J, M )
∗ location of J~
NOT the same! distributions
∗ location of internuclear axis
# of nodes
locations of nodes ] surfaces
where is the internuclear axis?
“reduced” pictures of ψJ,M (θ, φ)
Rotor is free
bond length
V (r 6= r0 , θ, φ) = ∞
?
V (r = r0 , θ, φ) = 0,
H
b = Tb
p̂2
for 1–D Tb = linear momentum
2µ
For rotor we want angular rather than linear momentum. From classical mechanics:
~ = ~r × p~
L
6
......
.......
.........
.....
......
ω
......................................
6
..... p1
......
....
I ....
. ...
• • •...
..
r1 ⊥ p1 , r2 ⊥ p2
m2 r2 r1 m1
b2
L
Tb = .
2I
Now we have a mass point µ (at r0 from origin), where bond axis points at the mass
point, µ
5.61 Fall 2017 Lecture #17 Page 4
6Z
t
θ
.................................................
.......
.....
....
...
...
µ
R project onto the X, Y plane
r0
-
@ Y
@
.......
........ .....
.......... .......@
.............................................
X φ @
@
}2
2
ASA: get 1 ∂ ∂ 1 ∂
T =−
b sin θ + 2
XY Z → rθφ 2I sin θ ∂θ ∂θ sin θ ∂φ2
looks bad!
Hψ
b = Tbψ = Eψ
We really do not want to do this in detail because we have little reason to actually look
at the Y (θ, φ) eigenfunctions. THIS SHOULD BOTHER YOU!
Outline of Steps
separation of variables
standard process — arrange θ stuff on LHS, φ stuff on RHS. Then divide both sides by
Θ(θ)Φ(φ).
A lot of algebra
5.61 Fall 2017 Lecture #17 Page 5
2
sin θ ∂ ∂ 2 1 ∂
sin θ Θ(θ) + β sin θ = − Φ(φ)
Θ(θ) ∂θ ∂θ Φ(φ) ∂φ2
| {z } | {z }
only θ only φ
2IE
β≡ collecting constants
}2
both sides must equal same constant: call it m2
2 separate equations:
2 separation constant
1 ∂ ?2
1. φ: 2
Φ(φ) = −m Easy to solve
Φ(φ) ∂φ
sin θ ∂ ∂
2. θ: sin θ Θ(θ) + β sin2 θ = m2 Leads to Legendre Equation
Θ(θ) ∂θ ∂θ
∂ 2Φ
= −m2 Φ(φ)
∂φ2
Φ(φ) = Am eimφ m = 0, ±1, ±2, Am is normalization constant
Φ(φ) = Φ(φ + 2mπ) periodic boundary condition
Am = (2π)−1/2 ← HOW DO WE GET THIS?
Notice that eimφ is complex
Can convert to real functions by 2−1/2 [eimφ ± e−imφ ]. Are these eigenstates?
Turns out we exchange the all-real functions of the geometric picture for a picture of the
eigenstates of L
bz .
# nodes in XY '$
plane
φ=0
&%
m=1
π π
cos φ = 0 @ = mφ φ =
2 2m
same nodal plane if m = 1
3π π
@ = mφ φ =3
2 2m
m is # of nodal planes thru XY plane.
5.61 Fall 2017 Lecture #17 Page 6
2nd differential equation for Θ(θ) is more complicated. Legendre Equation: can look at
notes. Note that the Θ DE depends on the value of m.
Pictures
But we want memorable pictures and intuition–guiding cartoons! See McQuarrie, page
286 for table of YLm (θ, φ) [at end of these notes].
Vector Model
6J
• ? •
1 C.M. 2
2. θ, φ are the lab frame coordinates of a fictitious particle of mass µ moving on the
surface of a sphere of radius r0 . They are also the coordinates of one end of the rotor
axis where the rotation is about the center of mass along this axis.
3. Key questions:
J
α
JZ YJM = |{z}
}M YJM
length of projection of J~ on Z
* Length of J~
D E1/2
|J| = [J · J]1/2 = ~J 2
J2 YJM = }2 J(J + 1)YJM
|J| = }[J(J + 1)]1/2 ≈ }(J + 1/2)
J
α
}M M
hcos αi =
}[J(J + 1)] 1/2
≈
J
CRUCIAL INSIGHT
Where is the internuclear axis in lab for a specified tilt of J~ from laboratory Z axis?
6JkZ
• •
molecular internuclear axis is rotating in XY plane
-
“frisbee”
-
Z
“helicopter”
M = ±J molec. axis different kinds
of collisions
molecular axis is in XY plane is more along Z
5.61 Fall 2017 Lecture #17 Page 9
Polar Plots
These are not the solutions of the (r, θ, φ) full 3D Schrödinger Equation. They are a way
of representing a 3D object in 2D.
xy plane
etc. J > 1
s p
spherical 3 dumbbells with axis along X, Y , and Z
L # surfaces
0(s) 0
1(p) 1
2(d) 2
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