Published on 02 July 2015 on https://pubs.rsc.org | doi:10.

1039/9781782620198-00001

CHAPTER 1

Scattering Experiments and

Classical Theory of Atom–Atom
Scattering
Downloaded on 4/21/2020 9:19:16 PM.

1.1 Crossed Atomic and Molecular Beams

We wish to investigate how atoms and molecules interact with each other in
the most fundamental manner. What happens when they closely approach
each other or collide? As molecules are far too small to see and the time-
scale of their collisions is very short, we resort to making them collide with
each other under strictly controlled conditions and examining the results in
as much detail as we can. Figure 1.1 shows a schematic of a crossed atomic
beam apparatus.1
To the left hand side of the diagram there is a sophisticated analyzer which
detects the products of the collision. The “quadrapole mass filter” selects
products of a defined mass and the chopper permits the determination as
to when the products arrive at the detector. From this it will be possible to
determine the speed and kinetic energy of the products. The detector assem-
bly remains fixed as it is the most complex component of the apparatus. To
the lower right hand side of the diagram are the two atomic or molecular
beam sources. These are at some fixed angle, normally 90◦ , relative to each
other and can be rotated with respect to the detector assembly. This permits
the measurement of the angular variation of the reaction probability (i.e. the
differential cross section).
The heart of the apparatus is the collision region where the two beams
cross and the collisions take place. This region is maintained under the
greatest attainable vacuum so as to exclude any unwanted molecules.

RSC Theoretical and Computational Chemistry Series No. 7

Theory of Molecular Collisions
By Gabriel G. Balint-Kurti and Alexander P. Palov
C Gabriel G. Balint-Kurti and Alexander P. Palov, 2015

Published by the Royal Society of Chemistry, www.rsc.org

1
 View Online

2 Chapter 1
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001
Downloaded on 4/21/2020 9:19:16 PM.

Figure 1.1 Diagram of a crossed molecular beam machine. Redrawn figure repro-
duced with permission from J. D. McDonald, P. R. LeBreton, Y. T. Lee
and D. R. Herschbach, J. Chem. Phys., 1972, 56, 769. Copyright 1972, AIP
Publishing LLC.1 DOI: 10.1063/1.1677230.

1.2 Classical Theory of Atom–Atom Elastic

Scattering
1.2.1 Hard Sphere Collisions
Let us now consider what happens when two atoms collide. Figure 1.2 shows
two atoms traveling towards each other. This is what a collision would look
like in the center-of-mass reference frame. We will discuss the difference
between the “laboratory frame” and the “center-of-mass” frame a little later.
In the center-of-mass frame the collision partners travel directly towards
each other. The distance “b” in the figure is called the impact parameter and
is the hypothetical distance of what would be the closest approach of the cen-
ters of the two atoms if there were no interaction between them. If the atoms
were hard spheres then they would either collide or miss each other entirely.
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 3

Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

Figure 1.2 Two atoms colliding; “b” is the impact parameter.

Downloaded on 4/21/2020 9:19:16 PM.

Figure 1.3 Grazing collision between two hard sphere atoms illustrating the con-
cept of a collision cross section.

They would collide if the impact parameter was smaller than the sum of the
radii of the two spheres.
Figure 1.3 shows a collision in which the two atoms just graze each other.
If the impact parameter were any larger, then the atoms would miss each
other entirely and there would be no collision. The maximum value of the
impact parameter for a collision to occur is the sum of the radii of the two
atoms, b Z r1 C r2 . If the projected path of atom 1 lies anywhere within the
area of the circle shown in Figure 1.3 then a collision will take place. The area
of this circle is called the collision cross section, s Z pR2 , where R Z r1 C r2 .
Let us now consider hard sphere collisions in greater detail. What is the
angle of scattering of the atoms after the collision? Figure 1.4 illustrates
what happens when two “hard sphere” atoms collide. When their surfaces
touch they bounce off each other like two billiard balls. The angle that the
direction of impact makes with the normal to the surface (a) is the same as
that made by the recoil velocity direction to this normal. This is termed spec-
ular reflection. The “scattering angle” is shown as q in Figure 1.4. From the
figure we see that
b Z R sin a, (1.1)
 View Online

4 Chapter 1
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001
Downloaded on 4/21/2020 9:19:16 PM.

Figure 1.4 Collision between two hard sphere atoms showing the scattering angle q.

where R Z r1 C r2 , and also

q C 2a Z p, (1.2)

and therefore
 
pKq q
b Z R sin Z R cos . (1.3)
2 2

All the atoms colliding with an impact parameter b to b C db are scattered

into scattering angles q to q C dq. The cross section for scattering into polar
angles q to q C dq is therefore
   
q q dq
2pb|db| Z 2pR cos R sin
2 2 2
1
Z pR2 sin q dq. (1.4)
2
dq
The absolute value signs have been introduced as is negative and the
db
cross sectional area is a positive quantity.
The “differential cross section” is defined as the flux of atoms scattered
into a given solid angle (dU Z sin q dq df) divided by the incident flux of
atoms. In the present case we have not considered the azimuthal angle, f.
We have in effect integrated over this angle. The solid angle, integrated over
all f, is 2p sin q dq. The differential cross section for scattering into a solid
angle dU is therefore

ds R2
Z . (1.5)
dU 4
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 5

The integral of the differential cross section over all angles must be equal
to the total or integral cross section
Z Z p Z 2p
ds ds
dU Z sin q dq df
dU 0 0 dU
Z 2p
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

R2 p
Z
Z sin q dq df
4 0 0
R2
Z 4p Z pR2 . (1.6)
4

1.2.2 Scattering Under the Influence of a Potential

Figure 1.2 shows a schematic of two atoms colliding. The position of each
atom is described by a vector with three spatial components r 1 and r 2 . Thus
the system overall requires six position coordinates to fully describe it. As
Downloaded on 4/21/2020 9:19:16 PM.

the forces determining the scattering of the atoms depend on the magnitude
of the distance between the two atoms, r Z |r 2 K r 1 |, it seems reasonable to
change coordinates to r, the position of atom 2 relative to atom 1, and R, the
position of the center-of-mass
r Z r2 K r1 ,
m1 r 2 C m2 r 1
RZ . (1.7)
m1 C m2
Classical mechanics is based on Newton’s laws of motion and these are
generally expressed in terms of the Cartesian (i.e. x, y, z) coordinates of each
of the particles involved. When other types of coordinates are used or when
there are constraints on the motion then it is advantageous to use alter-
native formulations of classical mechanics. In the present case we will use
Lagrange’s equations of motion.2,3 These equations can be written as
 
d vL vL
K Z0 (1.8)
dt vq̇i vqi
where
L Z Kinetic energy K Potential energy
Z T K V, (1.9)
dqi
qi is a generalized coordinate and q̇i Z is its time derivative.
dt
Returning now to the specific case of the scattering of two atoms, we can
write the kinetic energy in the form
1 1
T Z m1 v21 C m2 v22
2 2
1 1
Z m1 ṙ 21 C m2 ṙ 22
2 2
1 2 1
Z M Ṙ C mṙ 2 (1.10)
2 2
 View Online

6 Chapter 1

where
M Z m1 C m2 ,
m1 m2
mZ (1.11)
m1 C m2
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

and the potential energy V is a function of only r Z |r|, so

1 2 1
L Z M Ṙ C mṙ 2 K V(r). (1.12)
2 2
Let us first examine the equations of motion for the motion of the center-
of-mass of the system, R Z R(X, Y, Z). The derivatives of the Lagrangian with
respect to the X coordinate and its time derivative are
vL
Z M Ẋ,
vẊ
Downloaded on 4/21/2020 9:19:16 PM.

vL
Z 0. (1.13)
vX
The equation of motion for X is therefore (see eqn (1.8))
d
(M Ẋ) Z 0 (1.14)
dt
or
d
X Z Ẋ Z constant. (1.15)
dt
Similar equations apply to the Y and Z components of the center-of-mass
vector. We see therefore that the velocity of the center-of-mass is constant.
The center-of-mass of the colliding pair moves through space with a constant
velocity which is not changed by the collision. The variables X, Y and Z are
called cyclic coordinates. The potential function does not depend on them
and this leads to the properties just mentioned.
There remain the three coordinates which describe the vector r. As the
potential depends only on r Z |r| it is natural to use the spherical polar co-
ordinates r, q and f to define the vector r. In terms of these coordinates the
expression for the kinetic energy is2,3
1 2 1
T Z M Ṙ C mṙ 2
2
 2   
1 1  2 
2 2 2
m ṙ C rq˙
2


Z M Ẋ C Ẏ C Ż C . (1.16)
2 2
We notice immediately that the azimuthal angle, f, does not appear any-
where. It is therefore constant and is not changed by the collision. The
polar angle, q, appears only as a time derivative in the kinetic energy. The
Lagrangian equation of motion for q is therefore
 
d vL vL
K Z 0. (1.17)
dt vq˙ vq
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 7

vL
As Z 0 we see that
vq
vL
Z constant. (1.18)
vq˙
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

vL
The quantity is known as pq , the generalized momentum conjugate to q
vq˙
vL
pq Z
vq˙
˙
Z mr2 q. (1.19)

This quantity pq is the orbital angular momentum and in the present case of
a collision between two partners without any internal structure it is a con-
served quantity. We will, for the moment, denote it by the symbol `. If the
Downloaded on 4/21/2020 9:19:16 PM.

interaction potential was zero, then the closest distance two atoms would
approach each other would be the impact parameter, b, and this would be
equal to r at this point. The speed of the one atom relative to the other at this
point is rq˙ Z bq.
˙ As there is no potential in this hypothetical case the relative
speed of the two atoms is just the original velocity v. So we can write

` Z pq
Z mr2 q˙
Z bmv. (1.20)

Now let us consider the Lagrangian equations of motion for r. From

eqn (1.8), (1.9) and (1.16) we obtain
 
d vL vL
K Z 0,
dt vṙ vr
d vV
(mṙ) K mrq˙ 2 C Z0 (1.21)
dt vr
or, using eqn (1.20), we obtain
 2
d ` vV
(mṙ) K mr 2
C Z 0,
dt mr vr
`2
 
v VC
d 2mr2
(mṙ) Z K . (1.22)
dt vr
This is the equation of motion for a particle of mass m in one dimension
`2
moving in an effective potential of V C . The total energy of the system
2mr2
is also conserved. As the energy associated with the motion of the center-
of-mass is constant (see eqn (1.15)), the energy associated with the relative
motion must also be constant. The kinetic energy for the relative motion of
 View Online

8 Chapter 1

the two atoms is given by the second set of curly brackets in eqn (1.16). We
see therefore that the energy of relative motion is
  2 
1
E Z m ṙ2 C rq˙ C V(r)
2
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

1 1
Z mṙ2 C mr2 q˙ 2 C V(r)
2 2
 2
1 2 1 2 `
Z mṙ C mr C V(r)
2 2 mr2
`2
 
1 2
Z mṙ C V(r) C . (1.23)
2 2mr2

From eqn (1.22) and (1.23) we see that the one-dimensional equation of
motionfor r corresponds
 to a particle of mass m moving in an effective poten-
`2 `2
Downloaded on 4/21/2020 9:19:16 PM.

tial of V(r) C . The extra term, , is referred to as the centrifugal

2mr2 2mr2
potential.
Typically, two atoms attract each other at large distances and repel each
other when they approach each other very closely or collide. This leads to
a form of potential such as the analytic Lennard-Jones4 model potential in
eqn (1.24) and shown in Figure 1.5
  
s 12  s 6
V(r) Z 4 3 K . (1.24)
r r

Figure 1.5 Qualitative form of the inter-atomic potential between two atoms. The
analytic form used here is the so-called Lennard-Jones potential and the
parameters used are those applicable to the Ne + Ne collision pair of
atoms:5 3 Z 29.52 cmK1 , s Z 2.756 Å.
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 9

Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

Figure 1.6 Schematic trajectories of two colliding atoms for various values of the
impact parameter. The qualitative form of the interaction energy be-
tween the atoms is shown in Figure 1.5.

Let us now look at the scattering trajectories which arise for different im-
pact parameters. In Figure 1.6 we show three characteristic trajectories for
Downloaded on 4/21/2020 9:19:16 PM.

different values of the impact parameter. One of the atoms is fixed, and the
trajectory of the other atom relative to it is shown. Trajectory (A) shows a
head-on collision with an impact parameter of bZ0. We see that in this case
the incident atom bounces straight backwards and the relative motion of
the scattering partners has therefore been deflected by an angle of 180◦ .
Trajectory (B) shows a collision at an intermediate impact parameter. The
two atoms initially attract each other and the trajectory is deflected from its
original direction towards the other atom. They approach to a distance such
1 
that the initial energy of the relative motion mv2 equals the effective po-
 2
`2 mb2 v2
  
tential V(r) C Z V(r) C . At this point the radial velocity
2mr2 2r2
of the colliding atom is reversed and the atom ends up being deflected from
its original direction by some positive angle, which we denote here by q. The
point of closest approach of the two atoms is called the “classical turning
point”. At larger impact parameters (shown in trajectory (C)) the colliding
atom never approaches the other atom sufficiently closely to sample their
mutual repulsion, but only feels the long distance attraction. This leads to a
negative deflection.
The angle of deflection as a function of the impact parameter is called
the deflection function c(E, b). For very large impact parameters the
angle of deflection is zero (see Figure 1.6). The polar angle q on the other
hand starts at 180◦ or p, as this corresponds to the angle of the negative
Z axis. For this large impact parameter, straight line trajectory the final
polar angle is 0, the angle of the positive Z axis. The change in the angle
q is therefore p when the deflection function c(E, b) Z 0. From Figure 1.6
we see that the change of deflection angle during the course of the trajec-
tory is made up of two equal parts. If we start looking at the trajectory from
the point at which the collision partners are closest to each other, i.e. the
classical turning point r0 , then the total change of angle during the trajec-
tory is twice that which occurs during the final half of the trajectory. Let
 View Online

10 Chapter 1

us call this total change of angle Dq. The deflection function is therefore
c(E, b) Z p K Dq. The most straightforward way to compute the deflection
function is to recast eqn (1.20) and (1.23) so as to provide equations for q˙
and ṙ and to integrate them numerically from the classical turning point
outwards.
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

From eqn (1.20) we obtain

dq ˙ bv
ZqZ 2 . (1.25)
dt r
The relative velocity is related to the relative collision energy by
1
E Z mv2 . (1.26)
2
and combining eqn (1.25) and (1.26) we obtain
 1
Downloaded on 4/21/2020 9:19:16 PM.

dq b 2E 2
Z 2 . (1.27)
dt r m
From eqn (1.23) we can obtain an equation for ṙ
  21   12
`2

dr 2
Z ṙ Z G E K V(r) C . (1.28)
dt m 2mr2
From eqn (1.20) we can write
  12
2E 1
` Z bmv Z bm Z b (2mE) 2 . (1.29)
m
and substituting for ` in eqn (1.28) we obtain
  12   12
b2 E

dr 2
ZG E K V(r) C 2 . (1.30)
dt m r
Dividing eqn (1.27) by eqn (1.30) eliminates time from the equations and
we can then integrate from the classical turning point outwards to obtain an
equation for the deflection function2,3
Z ∞
dr
c(E, b) Z p K 2b p (1.31)
2 1 K b /r2 K V(r)/E
2
r0 r

where r0 is the classical turning point.

Three deflection functions for a Lennard-Jones4 model potential calcu-
lated using different collision energies are shown in Figure 1.7. At lower
energies the deflection function shows deflection angles more negative than
K180◦ or even K360◦ . This indicates the presence of orbiting type collisions
in which the atoms either circle around each other and finally spin off in the
direction opposite to their original direction of motion (c Z K180◦ ) or com-
pletely orbit each other so as to exit the collision moving in their original
directions (c Z K360◦ ).
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 11

Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001
Downloaded on 4/21/2020 9:19:16 PM.

Figure 1.7 The deflection function for the collision of two Ne atoms at various dif-
ferent relative collision energies, where 3 is the well depth (29.52 cmK1 ).
A Lennard-Jones potential is used to model the Ne + Ne interaction, see
Figure 1.5.

1.2.3 Singularities of a Differential Scattering Cross Section

As in the case of the collision of two hard spheres (see eqn (1.5)) we may
now define a differential scattering cross section. This is defined as the number
of atoms scattered into an increment of solid angle (dU), per unit time and
per unit incident flux of the collision partners. For an atom–atom collision,
in which the interaction potential is independent of angles, the azimuthal
angle f (i.e. the angle around the initial relative collision velocity) plays no
role and we in effect integrate the cross section over this angle. Indeed this
is the case in all situations where the target atom or molecule is not in some
way oriented in space (see however Chapter 10).
There is one, or maybe more than one, way that an incident atom can end
up being scattered through an angle q. This is illustrated in Figure 1.8 which
shows the incident atom being scattered into the same final direction by
the target atom while following two different scattering trajectories. In the
upper trajectory the collision has a large impact parameter and the deflection
is negative. The lower trajectory passes the target atom on the other side. It
suffers a positive deflection but ends up being scattered into the same scat-
tering angle as the upper trajectory. The scattering experiment cannot distin-
guish between a positive or a negative deflection. It just measures the abso-
lute value of the angle of deflection, |q|. For example, for an absolute value of
the deflection of 40◦ , we see from Figure 1.7 that there will be three different
values of the impact parameter which can lead to this scattering angle.
 View Online

12 Chapter 1
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

Figure 1.8 Schematic illustration of how two different trajectories can end up being
scattered into the same final scattering angle.
Downloaded on 4/21/2020 9:19:16 PM.

If we consider a small annulus of width db around a given impact

parameter b, all the incident projectiles passing through this annulus will be
scattered into a direction q to q C dq. The contribution of this small annulus
to the scattering cross section will therefore be
ds
2p sin q dq Z 2pb db (1.32)
dU
or
ds b
Z . (1.33)
dU dq
sin q
db
We see that the differential cross section will posses a singularity, i.e. blows
dq
up, whenever sin q Z 0 or Z 0. The first condition is known as the glory
db
effect which can be either forward for |q| Z 0, 2p, 4p, . . . or backward for
 dq 
|q| Z p, 3p, 5p, . . .. The second condition Z 0 is called the rainbow ef-
db
fect and corresponds to the slope of the deflection function (see Figure 1.7)
being zero. Clearly when the impact parameter, b, is very large there will
be no deflection; consequently, q Z 0 and the differential cross section will
become infinite. From Figure 1.7 we see that q is also zero for chosen en-
ergies when the deflection function passes from positive to negative in the
region of an impact parameter between 3 and 4 Å. The range of impact pa-
rameters around this value also contributes to the glory singularity in the
differential cross section in the vicinity of q Z 0. We will see later that the
quantum mechanical description of scattering leads to an interference be-
tween the scattering corresponding to these two ranges of impact parameters
(i.e. b Z ∞ and b ≈ 3–4 Å).
Figure 1.7 demonstrates that for scattering at a collision energy of 23 Z
59.04 cmK1 at impact parameters a little displaced to either side of the
minimum of the deflection function (at around 4 Å) there are two slightly
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 13

different values of b which lead to scattering into the same scattering angle,
close to but a little smaller than the rainbow angle (at which the slope of the
deflection function is zero). When we discuss this phenomenon using quan-
tum mechanics, we will see that the contributions from these two different
impact parameters lead to a characteristic interference pattern.
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

As we have seen from Figure 1.7, scattering into an angle of 40◦ can receive
contributions from three different impact parameters: two corresponding to
negative deflections and one to a positive deflection. We therefore need to
modify the expression for the differential cross section (eqn (1.33)) to take
account of these multiple contributions
ds X b
Z i  (1.34)
dU dq
i sin q
db i
where the summation is over all values of b which contribute to scattering
Downloaded on 4/21/2020 9:19:16 PM.

into the angle q.

Figure 1.9 shows the classical differential cross section for Ne + Ne scatter-
ing modelled using a Lennard-Jones interaction potential at the same three
collision energies as shown in Figure 1.7. For the high energy cross section
(collision energy Z 23 ≡ 59.04 cmK1 ) the main features of the cross section
are the two regions, at 0◦ and 62◦ , where the cross section becomes infinite.
The first of these arises because sin q in eqn (1.34) is zero and is referred to
dq
as glory scattering, while the second comes about because is zero and is
db

Figure 1.9 Differential cross section for Ne + Ne scattering as modelled using a

Lennard-Jones potential at the same three collision energies as in
Figure 1.7.
 View Online

14 Chapter 1

referred to as rainbow scattering. We see that the rainbow scattering angle

corresponds to the “bottom” of the deflection function plot (see Figure 1.7).
At lower energies the forward and backward glories dominate.
Another phenomenon that might occur at lower collision energies is an
orbiting collision. In such a collision the incident atom would circle com-
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

pletely around the target atom. This would show up in the deflection func-
tion plot (Figure 1.7) as a much deeper “well” with the deflection function
(c(E, b)) reaching negative values of K180◦ or more. This would give rise
to another singularity or infinity in the cross section at q Z |c(E, b)| Z 180◦
termed a backward glory. When treated quantum mechanically the glory
scattering gives rise to maxima rather than infinities in the differential cross
section and interference terms are present from the different contributions
to the scattering at 0◦ or at 180◦ .6
The integral cross section is obtained as the integral of the differential
cross section over all solid angles. When the potential extends to infinite
Downloaded on 4/21/2020 9:19:16 PM.

atom–atom separations, as do all realistic model potentials, and if we use

classical mechanics, then the integral cross section will always be infinite.
This is because no matter how large the impact parameter, the incident
atom will always experience a force and will be scattered to at least a small
extent. We will see that this problem is easily resolved with the use of
quantum mechanics.

1.3 The Laboratory and the Center-of-Mass

Reference Frames: Newton Diagrams
Figure 1.1 shows a typical crossed molecular beam machine. The two atomic
or molecular beams are shown at the bottom right hand side of the appara-
tus. They are shown as being at right angles to each other. While this is the
most common and simplest configuration to visualize, the angle between
the two beams may also be used as a variable in the design of the experi-
ment. Figure 1.10 shows a schematic of the collision between a beam of “A”
and “B” atoms, or molecules. The collision is shown in the “laboratory” or
“space-fixed” frame of reference. This is the frame in which we must make
our measurements, but it is not the most suitable frame for analyzing and
discussing the collision process. Each atom “sees” the other only in terms of
its motion relative to itself. Thus, for instance, the absolute velocity of the
atoms in the laboratory is not relevant to the mechanism or the outcome
of the collision. It is the relative velocity of the atoms to each other that is
important in this respect. This should be clear from our preceding discus-
sion where the collision was discussed in the center-of-mass reference frame
and it was always the relative velocity and the associated relative kinetic
energy that played the central role.
The coordinate of the center-of-mass of the system and the position of
atom “B” relative to atom “A” is defined in the same way as in eqn (1.7).
The relationship of the velocity of the center-of-mass and of the relative
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 15

Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001
Downloaded on 4/21/2020 9:19:16 PM.

Figure 1.10 Schematic diagram showing collision between atomic beams “A” and
“B” in laboratory frame.

Figure 1.11 Newton diagram showing relationship between center-of-mass and

laboratory velocities.

velocity to the initial velocities of the two atoms can be represented in a

very useful diagram known as a Newton diagram.7,8 The diagram depicts
the relationship between the laboratory and center-of-mass reference frames
and the limitations placed on the scattering process by the conservation
rules of energy and linear momentum. Figure 1.11 presents such a diagram.
 View Online

16 Chapter 1

vA and vB are the velocities of atoms “A” and “B” in the laboratory reference
frame. vC is the velocity of the center-of-mass (see eqn (1.7)). vC remains con-
stant throughout the collision even when inelastic and reactive collisions are
considered. v is the relative velocity (velocity of “B” relative to “A”). uA and uB
are the velocities of “A” and “B” in the center-of-mass reference frame (i.e. rel-
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

ative to the center-of-mass velocity). The magnitudes of the vectors uA , uB and

v are related by
mB
|uA | Z |v|
mA C mB
mA
|uB | Z |v|. (1.35)
mA C mB
After the collision we denote the velocities of “A” and “B” in the center-
of-mass by u0A and u0B and the relative velocity by v0 . These post-collision
velocities are shown in the upper panel of Figure 1.11. As we are currently
Downloaded on 4/21/2020 9:19:16 PM.

considering atom–atom elastic collisions the magnitudes of the velocities of

“A” and “B” in the center-of-mass reference frame remain the same after the
collision, but the directions of these velocities are altered by the collision. So
we can write
|u0A | Z |uA |
|u0B | Z |uB |
|v0 | Z |v|. (1.36)
The center-of-mass scattering angle q for the scattering of atom “B” is
shown in Figure 1.11. Figure 1.12 shows how the Newton diagram permits
us to relate the center-of mass and the laboratory scattering angle. We see
from the figure that there may be two different center-of-mass scattering an-
gles which lead to the same laboratory scattering angle. Figure 1.13 shows
two different final center-of-mass velocities of atom “B” which lead to the
same measured laboratory scattering angle. The Newton diagrams we have
presented here are somewhat simplified in that we have shown only in-plane
scattering. This is valid for atom–atom scattering, but in a more general case
there may also be some scattering out of the plane defined by the two initial
velocity vectors.

Figure 1.12 Newton diagram showing relationship between center-of-mass and

laboratory scattering angles.
 View Online

Scattering Experiments and Classical Theory of Atom–Atom Scattering 17

Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

Figure 1.13 Newton diagram showing the two different center-of-mass velocities of
atom “B” which lead to the same laboratory scattering angle.
Downloaded on 4/21/2020 9:19:16 PM.

The aim of a crossed molecular beam experiment is to measure the

scattering cross section. The theoretical discussion of this cross section
and its interpretation in terms of molecular interactions is most conve-
niently, or maybe necessarily, undertaken in the center-of-mass reference
frame. The transformation of the measured differential laboratory cross sec-
tion to the center-of-mass reference frame is quite a technical subject and we
refer the reader to the literature9–12 for further discussion.

References
1. J. D. McDonald, P. R. LeBreton, Y. T. Lee and D. R. Herschbach, Molecu-
lar beam kinetics: reactions of deuterium atoms with halogen molecules,
J. Chem. Phys., 1972, 56, 769.
2. H. Goldstein, Classical Mechanics, Addison-Wesley, Reading, Mas-
sachusetts, USA, 1950.
3. H. Goldstein, C. Poole Jr and J. Safko, Classical Mechanics, Addison-
Wesley, San Francisco, 2002.
4. D. M. Hirst, Potential Energy Surfaces, Molecular Structure and Dynamics,
Taylor and Francis, 1985.
5. F. Pirani, S. Brizi, L. F. Roncaratti, P. Casavecchia, D. Cappelletti and
F. Vecchiocattivi, Beyond the Lennard-Jones model: a simple and accu-
rate potential function probed by high resolution scattering data useful
for molecular dynamics simulations, Phys. Chem. Chem. Phys., 2008, 10,
5489.
6. K. W. Ford and J. A. Wheeler, Semiclassical description of scattering,
Ann. Phys., 1959, 7, 259.
7. D. R. Herschbach, Reactive collisions in crossed molecular beams,
Discuss. Faraday Soc., 1962, 33, 149.
8. D. R. Herschbach, Reactive scattering in molecular beams, Adv. Chem.
Phys., 1966, 10, 319.
 View Online

18 Chapter 1

9. F. A. Morse and R. B. Bernstein, Velocity dependence of the differential

cross sections for the scattering of atomic beams of K and Cs by Hg, J.
Chem. Phys., 1962, 37, 2019.
10. S. Datz, D. R. Herschbach and E. H. Taylor, Collision mechanics in
crossed Maxwellian molecular beams, J. Chem. Phys., 1961, 35, 1549.
Published on 02 July 2015 on https://pubs.rsc.org | doi:10.1039/9781782620198-00001

11. R. K. B. Helbing, Transformations and averaging processes for differ-

ential cross-section measurements at thermal energies, J. Chem. Phys.,
1968, 48, 472.
12. T. T. Warnock and R. B. Bernstein, Transformation relationships from
center-of-mass cross section and excitation functions to observable an-
gular and velocity distributions of scattered flux, J. Chem. Phys., 1968, 49,
1878.
Downloaded on 4/21/2020 9:19:16 PM.