University of Connecticut

OpenCommons@UConn
Chemistry Education Materials Department of Chemistry

7-12-2006

The Runge-Lenz Vector

Carl W. David
University of Connecticut, Carl.David@uconn.edu

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Recommended Citation
David, Carl W., "The Runge-Lenz Vector" (2006). Chemistry Education Materials. 14.
https://opencommons.uconn.edu/chem_educ/14
 The Runge-Lenz Vector

C. W. David
Department of Chemistry
University of Connecticut
Storrs, Connecticut 06269-3060
(Dated: February 5, 2007)

I. SYNOPSIS one for our purposes[3]. Let’s start with Cartesian coor-
dinates (named for the mathematician Rene Descartes).
The Runge-Lenz vector is a constant of the motion In this coordinate system the energy has the form:
which allows construction of ladder operator solutions for p2x + p2y + p2z Ze2
the Hydrogen Atom’s electron eigenfunctions and energy −p
eigenvalues. This paper discusses the precursor materi- 2µ x2 + y 2 + z 2
als to that discussion, developing equations originally ob-
where we (sneakily) moved to the center of mass of the
tained by W. Pauli. It also shows how the operator form
proton-electron system. The angular momentum in this
emerges without specialized arguments from the classical
same coordinate system is
form.  
 î ĵ k̂ 
~ = x y z 
 
L
II. INTRODUCTION
 
 p x p y pz 

The H-atom’s eigenfunctions and eigenenergies are which also can be written out in non-determinental form
usually obtained using differential equation methods, re- as
quiring study of Laguerre polynomials, etc.. Where ~ =L
L ~ x î+L
~ y ĵ+L
~ z k̂ = (ypz −zpy )î+(zpx −xpz )ĵ+(xpy −ypz )k̂
other problems in elementary quantum mechanics can be
solved in other ways, specifically using either ladder op- where we have implicitly defined the three components
erators or matrices, it is possibly surprising to find that ~ surreptitiously. Notice that we are using the unit
of L
most students do not know about the availability of these vectors which point in the x, y, and z directions respec-
(alternative) methods for the H-atom problem. In this tively.
piece, we discuss the precursor materials to the ladder
operator and matrix methods which can be used to solve
the H-atom problem [1]. III. THE POLAR COORDINATE
In order to proceed, we need to develop the Runge- REPRESENTATION OBTAINING r
Lenz [2] vector, which expands the number constants of
the motion of the H-atom from 4 to 7. The energy, E, is Now we turn to the polar coordinate form of these
a constant of the motion, as is the angular momentum, equations. We do this because the problem has spheri-
and this latter consists of 3 constants! Now, we add the cal symmetry, by virtue of the Coulomb potential form
Runge-Lenz vector, which, being a vector, is going to add (which only depends on r). To effect the transforma-
three more constants of the motion to the assortment. tion, we need to remember to transformation equations
First, we review the H-atom problem, classically, so between spherical polar coordinates and Cartesian coor-
that we can see where the Runge-Lenz vector fits in. We dinates. These equations are
start with the energy, which has the form (Z is the atomic
number, e is the charge on the electron): x = r sin θ sin φ
y = r sin θ cos φ
p2 −(Ze)(e)
+ z = r cos θ (3.1)
2m r
where we are writing the Coulomb potential using a for transforming from x, y, and z to r, θ, φ.The set of all
charge of Ze on the nucleus, e on the electron, and the six equations, in pairs, will be used over and over again
minus sign explicitly accounts for the fact that these two in what follows, so be ready to refer back to them. The
charges are opposite in sign. Notice, we have not yet Cartesian form of the energy
(really) specified the coordinate system.
p2x + p2y + p2z Ze2
Now the angular momentum −p
2µ x2 + y 2 + z 2
~ = ~r × p~
L
depends on the definition of ~r in Cartesian coordinates:
can be written in several different coordinate systems, as
can the energy, and part of our job is to pick the best ~r = xî + y ĵ + z k̂

Typeset by REVTEX
 2

which means that p must be The kinetic energy will be the dot product of p~ on itself,
  (aside from a constant):
p~ = µ ẋî + ẏ ĵ + ż k̂

[4] which implies

p~ = µ(v˙x î + v˙y ĵ + v˙z k̂)

2 2 2 !
p2x + p2y + p2z
  
p~ · p~ 1 dx dy dz 1
µ vx2 + vy2 + vz2


= = µ + + =
2µ 2µ 2 dt dt dt 2

all of which are saying the same thing. We finally in- ~

dA

Ze2

dr̂
=− κ (~r × p~) × r̂ +
troduce the so-called Runge-Lenz vector, employing the dt r2 dt
unit “r” vector (r̂ ≡ ~rr ):

~ = κL
A ~ × p~ + r̂ Now, we need a piece of calculus, viz.,

(where κ is a to-be-determined constant) so

~ × B)
(A ~ ×C
~ = (A
~ · C)
~ B~ − (B
~ · C)
~ A~
~
dA ~ × d~
= κL
p dr̂
+
dt dt dt
~ → ~r, B
where A ~ → p~, and C
~ → r̂,
since the angular momentum is itself a constant of the
motion.
~  2

dA ~ × −Ze r̂ + dr̂
= κL
dt r2 dt
IV. AN ASIDE CONCERNING THE TRIPLE
i.e., and using the definition of the angular momentum CROSS PRODUCT
vector, we have

~
dA

Ze2
 We need to obtain the “value” of the triple cross prod-
=− κ ~ × r̂ + dr̂
L uct.
dt r2 dt

 
 î ĵ k̂ 
~ ~ ~
 
(A × B) × C =  Ay Bz − Az By Az Bx − Ax Bz Ax By − Ay Bx 

 Cx Cy Cz 

which expands to ~ × B)
(A ~ ×C
~ =

~ × B)
~ ×C
~ = î (Az Bx Cz − Ax Bz Cz − Ax By Cy + Ay Bx Cy )
(A +ĵ (Ax By Cx − Ay Bx Cx − Ay Bz Cz − Az By Cz )
î ((Az Bx − Ax Bz )Cz − (Ax By − Ay Bx )Cy )
+k̂ (Ay Bz Cy − Az By Cy − Az Bx Cx + Ax Bz Cx )
+ĵ ((Ax By − Ay Bx )Cx − (Ay Bz − Az By )Cz )
+k̂ ((Ay Bz − Az By )Cy − (Az Bx − Ax Bz )Cx ) or, collecting terms

~ × B)
(A ~ ×C
~ =
 3
 
î Az Bx Cz + Ay Bx Cy + Ax Bx Cx − Ax Bz Cz − Ax By Cy − Ax Bx Cx −Ax Bx Cx + Ax Bx Cx
| {z } | {z }
+ĵ (Ax By Cx − Ay Bx Cx − Ay Bz Cz − Az By Cz )
+k̂ (Ay Bz Cy − Az By Cy − Az Bx Cx + Ax Bz )Cx )

which is, upon inspection, A. The time derivative of ~r

~ · C)
(A ~ B~ − (B
~ · C)
~ A~ (4.1) Next, we need the time derivative of r̂, i.e.,
This is the end of the aside, and we now return to the dr̂ d ~r
main derivation. = r
dt dt
which is
V. RETURN TO MAIN TEXT
1 ∂~r ∂1
= + ~r r
Our last result (using Equation 4.1) means that r dt dt
or
(~r × p~) × r̂ = (~r · r̂)~
p − (~
p · r̂)~r
1 p~ ∂(x2 + y 2 + z 2 )−1/2
the r.h.s. of which is = + ~r
rµ dt
   
~r · ~r p~ · ~r or
p~ − ~r
r r  
1 p~ 1 1 ∂x ∂y ∂z
= − ~r 2 2 x +y +z
rµ 2 (x + y + z 2 )3/2
2 ∂t ∂t ∂t
~
dA
 2 
Ze dr̂
=− κ (~r × p~) × r̂ +
dt r2 dt
1 p~ ~r · p~
 2  
Ze ~r · ~r
 
p~ · ~r
 
dr̂ − ~r ·
=− κ p
~ − ~r + (5.1) rµ µr3
r2 r r dt

~
dA

Ze2
 
~r · ~r
 
p~ · ~r
  
1 p~ ~r · p~

=− κ p~ − ~r + − ~r 3
dt r2 r r rµ µr

which becomes [5]

~
dA
 
1

p~ · ~r
  
1 1 ~r · p~

= − Ze2 κ


p~ − ~
r + p
~ − ~
r
dt r r3 µ r µr3

which means that if we can set this time derivative equal Therefore, the Runge-Lenz vector is
to zero, then we can declare A~ to be a constant of the
~= 1 ~
motion, so A L × p~ + r̂
Ze2 µ
which we have shown to be a constant of the motion in
 
1
−Ze2 κ + p~ = 0 the Kepler problem (H-atom problem). Now, we look at
µ
the dot product of this vector on the ~r vector, i.e.,
~ to have a zero time rate of change,
implying that if A ~ · ~r = 1
 
A ~ × p~ · ~r + r̂ · ~r
L
i.e., be a constant of the motion, then κ must be chosen 2
Ze µ
to make the quantity in brackets vanish, i.e.,
which is
 
1 ~ · ~r = 1 ~r
κ= A ((~r × p~) × p~) · ~r + · ~r
Ze2 µ Ze2 µ r
 4

and since we already know that which is

~ × B)
(A ~ ×C
~ = (A
~ · C)
~ B~ − (B
~ · C)
~ A~
1
ar cos θ = ((~r · p~)~
p · ~r − (~
p · p~)~r · ~r) + r
we obtain Ze2 µ

r2
 
~ · ~r = 1
A (~r · p~)~
p − (~
p · p~)~r) · ~r +
Ze2 µ r

and defining a as the magnitude of A ~ and r as the mag-

nitude of ~r, we have VI. L2
 2
1 r
ar cos θ = (~r · p~)~
p − (~
p · p~)~r) · ~r + Now, we need the form for L2 , i.e., what is
Ze2 µ r

   
 î ĵ k̂   î ĵ k̂ 
~ ·L
~ = L2 =  Lx Ly Lz  =  ypz − zpy zpx − xpz xpy − ypx
   
L   


 Lx Ly Lz   ypz − zpy zpx − xpz xpy − ypx 

which is,

L2 =
2 2
(x + y )p2z 2
+ (x + z 2
)p2y + (y 2
+ z )p2x
2
− 2xzpx pz − 2yzpy pz − 2yzpy pz =
r p − (xpx + ypy + zpz )2 = r2 p2 − (~r · p~)2
2 2
(6.1)

i.e., Figure 1 shows how this table is implemented. The ellipse

is being drawn with the filled focus being F1 , i.e., the one
L2 = r2 p2 − (~r · p~)2 where the Sun (proton) goes, and the other focus F2 is
”empty”.
We thus have
L2
ar cos θ = − +r
Ze2 µ
which is almost the traditional form. Rewriting, we have
L2 VII. SOME NEEDED COMMUTATORS
r(a cos θ − 1) = −
Ze2 µ
or Before proceeding, we need to develop some commu-
1 Ze µ 2 tators which will be useful later. We follow the paper of
= (1 − a cos θ) Pauli, whose English translation can be found at “Pauli,
r L2
Sources of Quantum Mechanics, (Ed. B. L. van der Waer-
which is one of the many forms of the elliptical orbit den), North-Holland Publ Co., 1967”. This is tiresome,
known since Kepler. but necessary, work.
How can we see this? Write
~ with ~r. We
First, we evaluate the commutator of L
1 1
= (1 − a cos θ) have, as an example
r b
where b = L2 /Ze2 µ. Assuming a < 1 we have
[Lx , x] = Lx x − xLx = (ypz − zpy )x − x(ypz − zpy ) = 0

1
 
θ r r
1 b i.e. [Li , xi ] = 0∀i.
 0 b (1 − a)
 
1−a

 
 π/2 1 What about
 b b 

1 b
 π b (1 + a)
 
1+a 
1
3π/2 b b
 5

[Lx , y] = Lx y − yLx = (ypz − zpy )y − y(ypz − zpy ) = ypz y − zpy y − y 2 pz + yzpy

which is,
−z(py y − ypy ) = −z(−ıh̄) = ıh̄z
Next, we do
[Lx , z] = Lx z − zLx = (ypz − zpy )z − z(ypz − zpy ) = ypz z − zpy z − yzpz + z 2 py = −ıh̄y
and
[Ly , x] = Ly x − xLy = (zpx − xpz )x − x(zpx − xpz ) = zpx x − xpz x − xzpx + x2 pz

which is

z(px x − xpx ) = −ıh̄z

[Ly , z] = (zpx − xpz )z − z(zpx − xpz ) = −x(pzz − zpz ) = −x(−ıh̄) = +ıh̄x

Next, we need the commutators of the angular momentum with the momentum, i.e., what is
[Lx , px ] =?
with the clear answer, zero. Then, what is
[Lx , py ] = Lx py − py Lx = (ypz − zpy )py − py (ypz − zpy ) = pz (ypy − py y) = ıh̄pz

We summarize our commutators (so far) as VIII. MORE COMMUTATORS

[Lx , x] = 0
Next, we remind ourselves of the commutators in the
[Ly , y] = 0 ~ system. We had
L
[Lz , z] = 0
[Lx , y] = ıh̄z = -[Ly, x]
 
 î ĵ k̂ 
 
[Ly , x] = -ıh̄z = Lx , y]  x y z 
 
[Lx , z] = ıh̄x = - [Lz , x]  
 pz p y p z 
[Lx , py ] = ıh̄pz
[Lx , pz ] = -ıh̄py ~
as the definition of L.
[Lx , px ] = 0
We then have, for example

[Ly , Lz ] = Ly Lz − Lz Ly = (zpx − xpz )(xpy − ypx ) − ((xpy − ypx )(zpx − xpz ))

which is, expanding the two products
z }| { z }| {
= zpx xpy − zpx ypx − xpz xpy +xpz ypx − (xpy zpx − xpy xpz − ypx zpx +ypx xpz )
| {z } | {z }
which equals, canceling,
zpy (px x − xpx ) − ypz (px x − xpx ) = −ıh̄(zpy − ypz ) = +ıh̄Lx

IX. SECTION 2 Now we need to obtain the commutators of the momen-

We have, using a sophisticated notation,

     
 î ĵ
 k̂   î(Ly z − Lz y)   îh̄Lx 
~ ⊗L
L ~ =  Lx Ly Lz  =  ĵ(Lz x − Lx z)  =  ĵh̄Ly 
    
     
 Lx Ly Lz   k̂(Lx y − Ly x   k̂h̄Lz 
 6

tum with the radius (remember, r = |~r|). Since [x, r] = 0 X. SECTION 3

(and the same for y and z, we have
∂r We had from Equation 9.2
[px , r] = px r − rpx = −ıh̄ + rpx − rpx
∂x ~r
which is p, ~r] = −ıh̄ = −ıh̄∇r = −ıh̄r̂
[~ (10.1)
r
x
[px , r] = −ıh̄ (9.1) and, for any function, we would have
r
from which we generalize in vector notation ( Equation p, f (~r)] = −ıh̄∇f (~r)
[~ (10.2)
34, Pauli)
so
~r
p, ~r] = −ıh̄
[~ (9.2) ~r
r p, r̂] = −ıh̄∇ ·
[~ (10.3)
or, said another way, r

p, f (r)] = −ıh̄∇f (r)

[~ (9.3) We know that

Following Pauli, we obtain the expression for the radial ∂xî ∂y ĵ ∂z k̂

∇ · ~r = î + ĵ + k̂ (10.4)
momentum, pr . We know that and alternative form of ∂x ∂y ∂z
the time dependent Schrödinger Equation involving com-
mutators is which equals three (3)! Further

[E, Φ(~r)] = −ıh̄Φ̇(~r) (9.4) 1 ∂(x2 + y 2 + z 2 )−1/2

∇ = î + ··· (10.5)
which is the way we know if something is a constant of the r ∂x
motion, since operators which commute with the energy which yields
are time-stationery.
So 1
∇ = −î(x2 + y 2 + z 2 )−3/2 x + · · ·
pr r
[E, r] = −ıh̄ṙ = −ıh̄ (9.5)
m which leads to
which means that
ı 1 x
pr = m [E, r] ∇ = −î 3 + · · ·
h̄ r r
and we then proceed to evaluate the commutator itself, which leads to
i.e., 1 ~r r̂
1 ∇ =− 3 =− 2 (10.6)
[E, r] = p2x + p2y + p2z r − r p2x + p2y + p2z



r r r
2µ
By explicit differentiation then, substituting Equation
We have (using only the first (x) term and Equation 9.1) 10.4 into the r.h.s. of Equation 10.3 we have
p2x r − rp2x = px (px r) − (rpx )px ~r 1 1
∇· = ∇ · ~r + ~r · ∇
i.e., r r r
x x which is, using Equation 10.6
= px (rpx − ıh̄ ) − (px r + ıh̄ )px
r r
~r 3 ~r 2
x x ∇· = − ~r · 3 = (10.7)
= px rpx −px ıh̄ − px rpx −ıh̄ px r r r r
| {z } r | {z } r
so, the commutator is
x x 

= −ıh̄ px + px 1
r r p, r̂] = −2ıh̄
[~ = −2ıh̄r̂ (10.8)
r
which becomes, for the three components actually re-
quired Pauli’s intermediate Equation between 44 and 44’.
1
[E, r] = −ıh̄ p · r̂ + r̂ · p~)
(~
2µ XI. SECTION 4

1 We will need
pr = p · r̂ + r̂ · p~)
(~ (9.6)
2 x x x
Pauli’s Equation 44. [px , ] = pz − pz
r r r
 7

i.e., as usual, for an arbitrary function f, We will also need

∂ xf ∂ xf
 
x x x x ∂f x x ∂f
[px , ] = pz − pz = −ıh̄ r − (−ıh̄) [pz , ]f = −ıh̄ r − −ıh̄
r r r ∂x r ∂x r ∂z r ∂z
which is which simplifies:
f x2 x ∂ 1f ∂1 ∂f
−ıh̄ + ıh̄ 3 f (11.1) [pz , ]f = −ıh̄x r + ıh̄f r = −ıh̄
r r r ∂z ∂z ∂z
Adding the three terms contributing to the total commu- i.e.,
tator we have
x z
1 x2 + y 2 + z 2 1 [pz , ] = +ıh̄x 3 (12.2)
p, r̂] = −3ıh̄ + ıh̄
[~ = −2ıh̄ r r
r r 3 r XIII. SECTION 6
This is a little deceiving, so we will work out a few terms.
We will also need (doesn’t this ever end?)
∂yf
 
y y ∂f
[px , ]f = −ıh̄ r − −ıh̄ y ∂ ry3 f y

∂f

r ∂x r ∂x [px , 3 ]f = −ıh̄ − 3 −ıh̄
r ∂x r ∂x
i.e.,
i.e.,
∂ 1f
 
y y ∂f
[px , ]f = −ıh̄y r − −ıh̄ f  
r ∂x r ∂x y ∂ 3 y ∂f
[px , 3
]f = −ıh̄y r − 3 −ıh̄
r ∂x r ∂x
for any function “f”, which is, upon expansion,
or
∂ 1r
 
y y ∂f y ∂f
[px , ]f = −ıh̄yf − ıh̄ − −ıh̄ y ∂ r13
r ∂x | r{z∂x} r ∂x [px , ]f = −ıh̄yf
| {z } r3 ∂x
which is, upon cancellation which equals
y yx y y y y

3xy

[px , ]f = −ıh̄ 3 = px − px (11.2) px − p x = −ıh̄ − (13.1)
r r r r r3 r3 r5

Also, we have
XII. SECTION 5
∂ rx3 f
 
x x ∂f
We will need the “converse” of the last result: [px , 3
]f = −ıh̄ − 3 −ıh̄
r ∂x r ∂x
∂ xf
 
x x ∂f
[py , ]f = −ıh̄ r − −ıh̄
r ∂y r ∂y ∂ x3
 
x x ∂f x ∂f
[px , 3
]f = − ıh̄ 3 −ıh̄ r f − 3 −ıh̄
which simplifies a bit to r r
| {z }∂x ∂x r ∂x
| {z }
x ∂ 1f x ∂f ∂1 which equals
[py , ]f = −ıh̄x r + ıh̄ = −ıh̄f r
r ∂y r ∂y ∂y
3x2
 
x x  x
i.e., px − p x = −ıh̄ − − ıh̄ − (13.2)
r3 r3 r3 r5
x y
[py , ] = +ıh̄x 3 (12.1) We make a table of these values for future use:
r r
 8

[px , r] px r − rpx −ıh̄ xr Equation9.1

[~p, r̂] p~ · r̂ − r̂ · p~ −2ıh̄r̂ Equation10.8
2
[px , xr ] px xr − xr px −ıh̄( 1r − xr3 ) Equation11.1
[px , yr ] px yr − yr px ıh̄ yx
r3 Equation11.2
xy
[py , xr ] x x
py r − r py ıh̄ r3 Equation12.2
[px , ry3 ] y y xy
 
px r 3 − r 3 px ıh̄

3 r 5

Equation13.1
x2
[px , rx3 ] x x 1
px r3 − r3 px −ıh̄ r3 − 3 r5 Equation13.2
[py , xr ] py xr − xr py −ıh̄(− xy
r3 ) Equation12.2

XIV. USING ALL THE PRECEDING since

MATERIALS
px x − xpx + py y − ypy + pz z − zpz = −3ıh̄
So, using Equation 9.6 and Equation 10.7 we have
  so
1 1 2
pr = (~ p · r̂ + r̂ · p~) = p~ · r̂ + p~ · r̂ + ıh̄
2 2 r pr r − rpr = −3ıh̄ + 2ıh̄ = −ıh̄

i.e., Pauli’s Equation 46. We know that from Equation 9.6

1 1
p · r̂ + ıh̄)
pr = (~ pr = (~ p · r̂ + r̂ · p~)
r 2
and from Equation 10.8
while doing things in the other order we have
1
1 p, r̂] = −2ıh̄
[~ = −2ıh̄r̂
pr = (r̂ · p~ − ıh̄) r
r
so
Right operating with r we have
 
1 1 1
p · r̂ + ıh̄)
pr r = (~ pr = p~ · r̂ + p~ · r̂ + 2ıh̄ = p~ · r̂ + ıh̄
2 r r
while left operating with r we have
Pauli’s equation 44’.
rpr = (r̂ · p~ − ıh̄) Lastly, we ask, what is

Adding these last two we have dr̂

?
dt
p~ · r̂ + r̂ · p~ = pr r + rpr
which we answer the same way, using the commutator
while subtracting, we have of the r unit vector with the energy, i.e., [E, r] which we
obtained in Equation 9.5, so now we form [E, r̂] (following
p~ · r̂ − ~r · p̂ = pr r − rpr + 2ıh̄ Pauli, we do the x-component only):

 
dr̂ ı 1 n 2 x x 2   2 x x 2   2 x x 2 o
= p x − p x + py − p y + pz − p z (14.1)
dt x h̄ 2µ r r r r r r
which we re-write as
 
dr̂ ı 1 n  x x  x x
= px px − p x − px − px px +
dt x h̄ 2µ r r r r
 9
 x x  x x
py p y − py − py − p y py +
 rx rx  rx r  o
x
pz pz − p z − p z − pz pz (14.2)
r r r r
which is, using Equations 11.2 and 12.2
1 x2 1 x2
        
dr̂ ı 1
= px −ıh̄ − 3 − ıh̄ − 3 px
dt x h̄ 2µ r r r r
 xy   xy 
−py ıh̄ 3 − ıh̄ 3 py
r xz   rxz  o
−pz ıh̄ 3 − ıh̄ 3 pz (14.3)
r r
which becomes
1 x2 1 x2
         
dr̂ ı 1 x
= px − ıh̄ − 3 + −ıh̄ − 3 px +
dt x h̄ 2µ r r r r r
 xy   xy 
py ıh̄ 3 − ıh̄ 3 py −
 xz r   rxz  o
pz ıh̄ 3 ) − ıh̄ 3 pz (14.4)
r r
i.e.,
  2
x + y 2 + z 2 − x2
  2
x + y 2 + z 2 − x2
  
dr̂ 1
= px + px + (14.5)
dt x 2µ r3 r3
 y y 
−x py 3 − x 3 py − (14.6)
r z r z o
−x pz 3 − 3 pz (14.7)
r r
which can be re-written as
  2
y + z2
  
dr̂ 1 xy xz
= px − p y 3 − pz 3 (14.8)
dt x 2µ r3 r r
 2 2
 
y +z xy xz
+ p x − p y − p z (14.9)
r3 r3 r3
which is Pauli’s Equation, call it 46b:
  2
y + z2
  2
y + z2
    yx yx   zx zx 
dr̂ 1
= px + p x − py 3 + 3 p y − pz 3 + 3 pz (14.10)
dt x 2µ r3 r3 r r r r

XV. SECTION 8

We now note the similarity between this expression and

a special cross product of angular moment by deriving

 
 î ĵ k̂ 
~ ⊗ ~r =  Lx Ly Lz  = Ly z − Lz y î + Lz x − Lx z ĵ + Lx y − Ly x k̂
       
L (15.1)
r3  x y z  r3 r3 r3 r3 r3 r3
 3 3 3 
r r r

where we remember that

 
 î ĵ k̂ 
 
~ =  x y z  = î(ypz − zpy ) + ĵ(zpx − xpz ) + k̂(xpy − ypx )
~r ⊗ p~ = L (15.2)
 
 px py p z 
 10

so, we obtain
 
 î ĵ k̂ 
~ ~r  
L ⊗ 3 =  (ypz − zpy ) (zpx − xpz ) (xpy − ypx )  = (15.3)
 
r  x y z

 
r3 r3 r3
 z y 
(zpx − xpz ) 3 − (xpy − ypx ) 3 î +
r r
 x z
(xpy − ypx ) 3 − (ypz − zpy ) 3 ĵ +
r r
 y x
(ypz − zpy ) 3 − (zpx − xpz ) 3 k̂ (15.4)
r r

y2 x2
 
or yz xz
p z 3 − py 3 − px 3 + p z 3 k̂ (15.6)
 z z y y r r r r
= zpx 3 − xpz 3 − xpy 3 + ypx 3 î +
r r r r 
 x x z z Of course, we are “only” doing the x-component, so we
xpy 3 − ypx 3 − ypz 3 + zpy 3 ĵ +
 r y r
y
r
x
r
x
have
ypz 3 − zpy 3 − zpx 3 + xpz 3 k̂ (15.5)
r r r r
z2 + y2
 
which we re-write as ~ ⊗ ~r
L = px
xz xy
− pz 3 − py 3
r3 x r3 r r
z2 y2
 
xz xy
= px 3 − pz 3 − py 3 + px 3 î +
r r r r which is half of what we need (part of Equation 14.10).
x2 z2
 
xy yz
py 3 − px 3 − pz 3 + py 3 ĵ + Next, we obtain
r r r r

 
~
r ~
⊗L i.e.
r3
x
 
   î ĵ k̂ 
~r ~

x y z

⊗ L =
 
r3 r3 r3 r3
 
x
 
 (ypz − zpy ) (zpx − xpz ) (xpy − ypx ) 
x
(15.7)

which is Since according to Newton’s second law for the H-atom

  version of Coulomb’s Law,
~r ~ y z
3
⊗ L = 3 (xpy − ypx ) − 3 (zpx − xpz ) (15.8)
r x r r
Ze × e
or p~˙ = − ~r
r3

z2 + y2
 
~r ~ xz xy
3
⊗ L =− 3
px + 3 pz + 3 p y
r x r r r it follows that the following vector has no time derivative:

which is the other half of what we need (part of Equation

14.10). 1 n o
~=
A L~ ⊗ p~ − p~ ⊗ L
~ + r̂ (15.10)
So, the final result is Pauli’s Equation 47 (in more 2mZe2
modern notation)
 
d~r 1 ~ ~r ~r ~ This is the infamous Runge-Lenz vector (in quantum me-
= L⊗ 3 − 3 ⊗L (15.9)
dt 2m r r chanical operator form).
 11

XVI. THE RUNGE-LENZ VECTOR AND THE where, of course, µ is the reduced mass of the proton-
LADDER OPERATOR FOR THE H-ATOM’S electron system (If Z is not one, our nucleus is not a
ELECTRON proton, and we need to worry about the appropriate value
of µ. Or, to be even more pedantic, even if Z=1 we
The Runge-Lenz vector in operator form, may also have to worry about the value of µ based on
which hydrogen isotope we are dealing with.) Anyway,
~= 1 ~ 
~ + r̂ we will be dealing with A~ as defined above, i.e., the three
A L ⊗ p
~ − p
~ ⊗ L (16.1)
2Ze2 µ components Ax , Ay , and Az . The ladder operators will
turn out to be A+ = Ax + ıAy and A− = Ax − ıAy so we
turns out to be the source of the ladder operator for the
need first to obtain the components of A, and then we
H-atom problem. For extra reference to what follows, one
need to figure out the commutators of those components,
can consult Borowitz, Fundamentals of Quantum Me-
both with each other, and with the Hamiltonian.
chanics, W. A. Benjamin Inc., 1967, or Pauli, Sources
of Quantum Mechanics, (Ed. B. L. van der Waerden), ~ are obtained by first expanding
The components of A
North-Holland Publ Co., 1967. the determinental

XVII. ~ WITH THE

COMMUTATOR OF A    
HAMILTONIAN  î ĵ k̂ 
  î(Ly pz − Lz py )
~ ⊗ p~ =  Lx Ly Lz  = 
L  ĵ(Lz px − Lx pz )  (17.1)

~ with the
We are going to need the commutator of A
 
 px py p z  k̂(Lx py − Ly px )
Hamiltonian of the problem,

h̄2 2 Ze2
Hop = − ∇ − or
2µ r

   
 î ĵ k̂ 
  î((zpx − xpz )pz − (xpy − ypx )py )
~ ⊗ p~ =  Lx Ly Lz  = 
L  ĵ((xpy − ypx )px − (ypz − zpy )pz ) 

(17.2)
 
 p x p y pz  k̂((ypz − zpy )py − (zpx − xpz )px )

so we have +k̂((ypz py − zp2y ) − (zp2x − xpz px )) (17.3)

~ ⊗ p~ = î((zpx pz − xp2 ) − (xp2 − ypx py )
L z y

+ĵ((xpy px − yp2x ) − (yp2z − zpy pz )) so, adding and subtracting appropriately we have

~ ⊗ p~ = î(zpx pz − xp2z − xp2y + ypx py + xp2x − xp2x )

L
+ĵ(xpy px − yp2x − yp2z + zpy pz + yp2y − yp2y ))
+k̂(ypz py − z(p2y + p2x + p2z ) + xpz px + zp2z ) (17.4)

so that, collecting terms, we have

~ ⊗ p~ = î(zpx pz − x(p2z + p2y + p2x ) + ypx py + xp2x )
L
+ĵ(xpy px + zpy pz + yp2y − y(p2x + p2z + p2y ))
+k̂(ypz py − z(p2y + p2x + p2z ) + xpz px + zp2z ) (17.5)

and which becomes +ĵ(xpy px + zpy pz + yp2y )

~ ⊗ p~ = î(zpx pz + ypx py + xp2 )
L x
 12

+k̂(ypz py + xpz px + zp2z ) like px xpx , i.e.,

−~r(~
p · p~) (17.6)
~ ⊗ p~ = −~r(~
L p · p~)
i.e., +î(px (zpz + ypy ) + px xpx + ıh̄px )
~ ⊗ p~ = −~r(~
L p · p~) + +ĵ(py (xpx + zpz ) + py ypy + ıh̄py )
î(px (zpz + ypy ) + xp2x ) +k̂(pz (xpx + ypz ) + pz zpz + ıh̄pz )
ĵ(py (xpx + zpz ) + yp2y ) and, collecting again
+k̂(pz (xpx + ypz ) + zp2z ) (17.7)
~ ⊗ p~ = −~r(~
L p · p~) + ıh̄~
p + p~(~r · p~) (17.8)
Using the commutators similar to px x − xpx = [px , x] =
−ıh̄ we convert terms such as xp2x = xpx px to something Next we need the same operators in reverse order:

   
 î ĵ k̂ 
  î(py Lz − pz Ly )
~ =  px py pz  = 
p~ ⊗ L  ĵ(pz Lx − px Lz ) 

(17.9)
 
 Lx Ly Lz  k̂(px Ly − py Lx )

   

 î ĵ k̂ 
 î(py (xpy − ypx ) − pz (zpx − xpz ))
~
p~ ⊗ L = 

px py pz  =  ĵ(pz (ypz − zpy ) − px (xpy − ypx )) 
  
(17.10)
 
 ypz − zpy zpx − xpz xpy − ypx  k̂(px (zpx − xpz ) − py (ypz − zpy ))
or, expanding
 
î(py xpy − py ypx − pz zpx + pz xpz )
~ =
p~ ⊗ L  ĵ(pz ypz − pz zpy − px xpy + px ypx ) 

(17.11)
k̂(px zpx − px xpz − py ypz + py zpy )
or, expanding again
 
î(x(p2y + p2z ) − py ypx − pz zpx + xp2x − xp2x )
~ =
p~ ⊗ L  ĵ(y(p2z + p2x ) − pz zpy − px xpy + yp2y − yp2y ) 

(17.12)
k̂(z(p2x + p2y ) − px xpz − py ypz + zp2z − zp2z )
which is
 
î(x(p2y + xp2z + p2x ) − py ypx − pz zpx − xpx px )
~ =
p~ ⊗ L  ĵ(y(p2z + p2x + p2y ) − pz zpy − px xpy − ypy py ) 

(17.13)
k̂(z(p2x + p2y + zp2z ) − px xpz − py ypz − zpz pz )
or, using the commutators, we obtain
 
î(x(p2y + xp2z + p2x ) − py ypx − pz zpx − (px x + ıh̄)px )
~ =
p~ ⊗ L  ĵ(y(p2z + p2x + p2y ) − py pz z − py px x − (py y + ıh̄)py ) 

(17.14)
k̂(z(p2x + p2y + zp2z ) − px xpz − py ypz − (pz z + ıh̄)pz )
which is
 
p · p~) − py ypx − pz zpx − (px x + ıh̄)px )
î(x(~
~ =
p~ ⊗ L p · p~) − py pz z − py px x − (py y + ıh̄)py ) 
 ĵ(y(~

(17.15)
p · p~) − px xpz − py ypz − (pz z + ıh̄)pz )
k̂(z(~
which can be re-written as
~ = ~r(~
p~ ⊗ L p · p~) − (~
p · ~r)~
p − ıh̄~
p (17.16)
 13

Turning back to Equation 16.1 and substituting Equation 17.16 and Equation 17.8 we obtain

~ ⊗ p~ − p~ ⊗ L
L ~ =
−~r(~
p · p~) + ıh̄~
p + p~(~r · p~) − [~r(~
p · p~) − (~
p · ~r)~
p − ıh̄~
p] (17.17)

which can be re-written as But

~ p −~
L⊗~ ~ = −2~r(~
p⊗L p ·~
p)+2ıh̄~ p(~r ·~
p +~ p ·~r)~
p)+(~ p (17.18)

p~(~r · p~) + (~
p · ~r)~
p=
+î(px (xpx + ypy + zpz ) + px xpx + py ypx + pz zpx )
+ĵ(py (xpx + ypy + zpz ) + py ypy + (px x + pz z)py )
+k̂(pz (xpx + ypy + zpz ) + pz zpz + (px x + py y)pz ) (17.19)

or, re-arranging

p~(~r · p~) + (~
p · ~r)~
p=
+î(px (xpx + ypy + zpz ) + px xpx + px (ypy − ıh̄ + px (zpz − ıh̄))
+ĵ(py (xpx + ypy + zpz ) + py ypy + ((xpx − ıh̄) + (zpz − ıh̄))py )
+k̂(pz (xpx + ypy + zpz ) + pz zpz + ((xpx − ıh̄) + (ypy − ıh̄))pz ) (17.20)

(why can we so blithely move py and pz from the rear to for the Runge-Lenz vector. We have
the front in the above equation?) which is

p~(~r · p~) + (~
p · ~r)~ p(~r · p~) − 2ıh̄~
p = 2~ p
~ · ~r = 1 ~ 
A L ⊗ p
~ − ıh̄~
p · ~r + r
so that Ze2 µ
r2
since r̂ · ~r is r . Continuing, we have
~ ⊗ p~ − p~ ⊗ L
L ~ =
2 {−~r(~
p · p~) + ıh̄~
p} + p~(~r · p~ − 2ıh̄~
p}
~
= 2L ⊗ p~ + 2ıh̄~ p (17.21) 1 ~  1
~ · ~r =
A L ⊗ p~ · ~r − p) · ~r + r
(ıh̄~ (18.1)
2
Ze µ Ze2 µ
where we have used Equation 17.8.
We finally obtain

~= 1 ~ ~ +r̂ = 1
 
~ ⊗ p~ − ıh̄~

which is
A 2
L ⊗ p~ − p~ ⊗ L 2
L p +r̂
2Ze µ Ze µ
(17.22)
which is Equation 51’ (according to the Pauli  
manuscript). î ĵ k̂
~r= 1 
A·~
 1
 Lx Ly Lz ·~r− 2 (ıh̄~
p)·~r+r (18.2)
Ze2 µ Ze µ
px py p z
XVIII. ANOTHER PAULI EQUATION

~ · ~r where we are looking for the

Now we ask what is A
quantum mechanical equivalent of the conic section rule i.e.,
 14

       
î ĵ k̂ x px x
~ · ~r = 1 
A ·
 Lx Ly Lz   y 
  
−
1
(ıh̄) ·
 py   y  + r
   
(18.3)
Ze2 µ Ze2 µ
px py p z z pz z

or, expanding
   
(Ly pz − Lz py ) x
~ · ~r = 1 
A (L p
z x − L p
x z ) ·
  
y −
1
p) · ~r + r
(ıh̄~ (18.4)
2
Ze µ
  
Ze2 µ
(Lx py − Ly px ) z

which is, expanding (and watching the order of operators carefully):

~ · ~r = 1
A (Ly pz x − Lz py x + Lz px y − Lx pz y + Lx py z − Ly px z) −
Ze2 µ
1
p) · ~r + r
(ıh̄~ (18.5)
Ze2 µ
which is

~ · ~r = 1
A (+Lx (py z − pz y) + Ly (pz x − px z) + Lz (px y − py x)) −
Ze2 µ
1
(ıh̄ (px x + py y + pz z)) + r (18.6)
Ze2 µ
or

~ · ~r = 1 1
−L2x − L2y − L2z −


A 2
(ıh̄ (px x + py y + pz z)) + r (18.7)
Ze µ Ze2 µ
and, in reverse order

  
x (Ly pz − Lz py )
~= 1 
~r · A  y  ·  (Lz px − Lx pz )  −
   1
(ıh̄~r) · p~ + r (18.8)
Ze2 µ Ze2 µ
z (Lx py − Ly px )

~= 1
~r · A (x (Ly pz − Lz py ) + y (Lz px − Lx pz ) + z (Lx zpy − Ly px )) −
Ze2 µ
1
(ıh̄ (xpx + ypy + zpz )) + r (18.9)
Ze2 µ
and, re-arranging (expanding)

~= 1
~r · A (xLy pz − xLz py + yLz px − yLx pz + zLx py − zLy px ) −
Ze2 µ
1
(ıh̄ (xpx + ypy + zpz )) + r (18.10)
Ze2 µ
~ i.e.,
It is easiest if we quickly obtain the commutators of ~r with L,

[x, Ly ] = x(zpx − xpz ) − (zpx − xpz )x

which is (since px x − xpx = −ıh̄)

[x, Ly ] = xzpx − x2 pz − zpx x + xpz x = zxpx − zpx x = z(xpx − px x) = z(ıh̄)

Similarly, we have

[y, Ly ] = 0
 15

which is true in general. Finally, we have

[z, Ly ] = zzpx − zxpz − zpx z + xpz z = −zxpz + xpz z = x(pz z − zpz ) = x(−ıh̄)

We summarize these results in the following table:

xLy − Ly x = ıh̄z
yLz − Lz y = ıh̄x
zLx − Lx z = ıh̄y
(18.11)
zLy − Ly z = −ıh̄x
xLz − Lz x = −ıh̄y
yLx − Lx y = −ıh̄z

Returning to Equation 18.10

~= 1
~r · A ((Ly x + ıh̄z)pz − (Lz x − ıh̄y)py +
Ze2 µ
(Lz y + ıh̄x)px − (Lx y − ıh̄z)pz +
(Lx x + ıh̄y)py − (Ly z − ıh̄x)px ) −
1
(ıh̄ (xpx + ypy + zpz )) + r (18.12)
Ze2 µ
or, expanding

~= 1
~r · A (Ly xpz + ıh̄zpz − Lz xpy + ıh̄ypy +
Ze2 µ
Lz ypx + ıh̄xpx − Lx ypz + ıh̄zpz +
Lx xpy + ıh̄ypy − Ly zpx + ıh̄xpx ) −
1
(ıh̄ (xpx + ypy + zpz )) + r (18.13)
Ze2 µ
which becomes

~= 1
~r · A (Ly (xpz − zpx ) + 2ıh̄(zpz + ypy + xpx )
Ze2 µ
+Lz (ypx − xpy ) + Lx (xpy − ypz )) −
1
(ıh̄ (xpx + ypy + zpz )) + r (18.14)
Ze2 µ
or

~= 1
−L2y − L2z − L2x + 2ıh̄(zpz + ypy + xpx ) −


~r · A 2
Ze µ
1
(ıh̄ (xpx + ypy + zpz )) + r (18.15)
Ze2 µ

or while from Equation 18.7

~= 1 1
−L2 + 2ıh̄~r · p~ − 2 ıh̄~r · p~ + r (18.16) ~ · ~r = − 1 L2 − ıh̄ p~ · ~r + r


~r · A 2 A (18.18)
Ze µ Ze µ Ze2 µ Ze2 µ
so, finally,
~=− 1 ıh̄
1 ıh̄ ~r · A 2
L2 + p · ~r + 3) + r
(~ (18.19)
~=−
~r · A L2 + ~r · p~ + r (18.17) Ze µ Ze2 µ
2
Ze µ Ze2 µ
Adding Equation 18.18 and 18.19 we have
and we note
~ = − 2 L2 + ıh̄ (+3ıh̄) + 2r (18.20)
~ · ~r + ~r · A
A
p~ · ~r = ~r · p~ − 3ıh̄ Ze2 µ Ze2 µ
 16

i.e., which is Equation 51 in Pauli’s manuscript.

~ · ~r + ~r · A
A ~ 1

3h̄2

=− 2 L2 + +r (18.21)
2 Ze µ 2

ϑ=π/2

1+a 1−a
ϑ=0
ϑ=π F2 F1

ϑ=(3π)/2

FIG. 1: The ellipse in planar polar coordinates.

[1] C. W. David, Am. J. Phys., 34,984(1966)
[2] There is some controversy about naming this vector quan-
tity, and we will follow standard procedure, and ref-
erence C. Runge, Vector Analysis, E. P. Dutton, New
York, 1919), Chap 11, Sec 5; and W. Lenz, Z. Phys.
24,197(1924). One should also consult H. Goldstein, Am.
J. Phys., 44, 1123(1976) and references therein. Finally, I
need to call attention to a paper by Blinder which uses our
work here, J. Chem. Ed., 78, 391(2001). Finally, in pass-
ing, in the year 2007, it seems appropriate to comment
that citing materials in the chemistry education literature
seems to be quite haphazard.
[3] Cartesian coordinates are the first choice, then spherical
polar coordinates if we are aiming to treat the isolated
atom’s bound states, then cylindrical coordinates is we
are interested in treating external fields, then elliptical
coordinates if we are interested in dealing with H2+ (and
we may have left out a few).
[4] the velocity can be invoked (in one dimension) we have:
dx
p = µv = µ
dt
[5] I am indebted to Prof. Liang Chen, physicist at the Uni-
versity of Ottawa, Canada, for pointing out an earlier error
in this manuscript concerning ~r · p
~, which I had declared
to be zero. Although this is true for circular orbits, Kep-
lerian orbits have this true only at certain points in space
(apogee and perigee). Therefore, the longer derivation has
been substituted for this spurious argument.