Quadrupole Mass Spectrometry

The Physics of Quadrupole Mass Spectrometry

The essential physical components of a quadrupole mass spectrometer consist of an
ionization chamber, accelerating electrodes, a physical apparatus consisting of four long
rods (colored green in the drawing below) with hyperbolic cross section, a geometrical
arrangement as shown in the figures below and a detector.

Figure 1a Figure 1b
Suppose that at the surface of the upper and lower hyperbolic rods the electrical potential
is given by
[ cos( )] / 2 U V t
when
2 2
0
y x r t + ,
and at the oppositely charged, left and right hyperbolic rods the potential is given by
[ cos( )] / 2 U V t
when
2 2
0
x y r t + ,
where U is a constant i.e. time-independent voltage, V is the maximum value of a time-
varying RF sinusoidal voltage and
2 f
where
f
is the frequency. In the evacuated
region between the rods (colored white) the electrical potential is given by the Poisson
equation
2
4 ,
where

is the charge density between the rods. Since there is no charge in that region,
the electrical potential satisfies the equation
2
0 .
The general solution to this equation is
2 2
( , ) x y a x b y + with 0 a b + i.e. the sum of
the constants
, a b
must add up to zero. The
and x y
coordinates are independent of each
other and can take on any values (within the white area) between the rods. We have
therefore
2 2
( , ) ( ) x y a x y ,
where the constant
a
can be determined from the boundary conditions given above. That
is to say, if the
y
values are those along the surface of the upper and lower hyperbolae
then
2 2
0
y x r t + and
[ cos( )] / 2 U V t
.
We get
2
0
[ cos( )] / 2 ( ) U V t a r and therefore the electrical potential is uniquely
determined by the relation
2 2
2
( )
( , ) [ cos( )]
2
o
x y
x y U V t
r

. Eq. (1)
If on the other hand, if the
x
values are given by
2 2
0
x y r t + and
[ cos( )] / 2 U V t
,
along the surfaces of the left and right hyperbolae. Under this condition one has
2
[ cos( )] / 2 ( )
o
U V t a r i.e. we get the same result as given above in Eq. (1). See
Appendix B for a further description of the electrical potential and its effect on the
motion. If a charged particle (atom, molecule) with position
, x y
is injected into the
evacuated region between the four rods and propelled down the
z
- axis (i.e.
perpendicular to the
, x y
plane) it will be subjected to a force
r
F
given by

r
e F .
From this and Eq. (1) we get Newtons equations of motion for a particle with charge
e
and mass m i.e.
2
2 2
0
( )
[ cos( )]
d x y
m e U V t
dt r

r i j
r r
r
,
or in terms of this vector equations components
2
2 2
0
2
2 2
0
2
2
[ cos( )]
,
[ cos( )]
,
0.
d x e U V t
x
dt m r
d y e U V t
y
dt m r
d z
dt

_


,
_

Notice that the particles motion along the z axis is not affected by the electric fields
and its speed along that axis is not changed.
Mathematical Detail
The differential equations which describe the motion of the charged particle along
either the x or the y-axis can be written as the single equation i.e.
2
2
[ 2 cos(2 )]
d f
a q f
d

, Eq. (2)
where

2 2 2 2
0 0
4 2
, , / 2

_ _


, ,
e e
a U q V t
r m r m
. Eq. (2.1)
If
f x
the constants
, a q
are defined above. On the other hand, if
f y
then
, and a q

are replaced by
, and a q
. The quantity

is a scaled time. Equation (2) had been

solved by Mathieu in 1868 in connection with the oscillations of an elliptically shaped
membrane. That is, the equation was known much earlier then the invention of the
quadrupole mass spectrometer by W. Paul in 1953. In order to understand the
functioning of a quadrupole mass spectrometer, one has to examine the solutions of the
Mathieu equation.
The general solution of the Mathieu equation can be shown to have the form
( ) ( ) f Ae F Be F

+
, Eq. (2.2)
where
, A B
are constants of integration. These constants are determined by the initial
values of the
and x y
coordinates and their corresponding velocity components.
Furthermore, the quantity

is a function of the constants

, and a q
alone and not the
initial conditions. The function F is a periodic function of the scaled time. The term

in
Eq. (2.2) is the all-important quantity. In general it can be a complex number i.e.
( , ) a q i +
, Eq.(2.3)
where i is the imaginary number and,
,
are real functions of
, and a q
. One can show
that stable solutions (i.e. ones which remain finite as

increases) exist only if the real

part of

i.e. 0 and the imaginary part of

i.e.

is not equal to an integer. Thus,
stable states exist only for certain special combinations of
and a q
. In all other cases,
the x and/or the y coordinates of the charge become very large as time increases.
Physically this means that in the stable cases, the particle oscillates in the x and y
directions within the free space between the quadrupoles and eventually exits that region
to be counted i.e. detected. In the unstable cases, the particle veers off in the x and/or y
direction, hits a quadrupole rod or exits laterally and is lost.
The Mathieu Functions
The case of the unstable oscillations, i.e. those which arise when

is equal to an
integer, is an interesting one in that, these produce curves in the
, a q
plane along which
stable solutions do not exist. In fact these values of
and a q
i.e. these curves
( ) aq
establish boundaries between regions where stable solutions do exist.
If Eq. (2) is rewritten in the following way i.e.
2
2
2 cos(2 )
d
q f a f
d

+
' ;

, Eq. ( 2.4)
we see that the Mathieu equation can be viewed as an eigenvalue problem. That is to say,
for a given value of
q
, only special values of
a
are allowed. These are called the
eigenvalues or characteristic values of the operator within the curly brackets in the
equation above. For each value of the eigenvalue
a
, there is a corresponding function
f

called an eigenfunction.
Since the cosine term on the left-hand side of the equation is periodic, and an even
function in

, the eigenfunctions must be either even or odd functions of the variable

.
In fact one can show that in this situation i.e. where
f
is an eigenfunction, the quantity

in Eq. (2.3) equals
0, or 1
. Hence,
a
becomes a function of
q
.
Furthermore, in the simplest case i.e. where
0 q
, the eigenfunctions which are just
cos( ) r
and
sin( ) r
are seen to be periodic with periods

or 2 and have eigenvalues

2
a r where,
r
is an integer i.e. 0, 1, 2, 3
L
.
To summarize for
0 q
,
2
cos( )
,
sin( )
r
r
f a r
r

'

.
In the cases where
0 q
, the even eigenfunctions of the Mathieu equation are denoted by
( , )
r
ce q
. These have period

if
r
is an even integer, and have period 2 if
r
is
an odd integer. The eigenvalues
a
associated with the
( , )
r
ce q
functions (these
correspond to the
0
case) are designated by
r
a
. The odd eigenfunctions
( , )
r
se q
(these correspond to the
1
case) have period

, if
r
is an even
integer and have period 2 if
r
is odd. The eigenvalues associated with the
( , )
r
se q
functions are designated by
r
b
.
In summary we have
( ) ( )
, ( )
( ) ( )
r r
r
r r
ce a q
f aq
se b q

' '

The first few eigenvalues and eigenfunctions have been displayed in the appendix of this
section. Mathieu called these eigenfunctions, elliptical cosine and elliptical sine functions
respectively and were seen as generalizations of the cosine and sine functions appearing in
the
0 q
case. See Appendix A for a look at the first few of these eigenfunctions and
eigenvalues.

These eigenvalues increase in value (for a given value of
q
) in the order
0 1 1 2 2 3
a b a b a b < < < < < L
Because of the different (even and odd) symmetries of the two solutions i.e.
( , )
r
ce q
and
( , )
r
se q
one can show that the curves
1
( ), ( )
r r
a q b q
+
cannot cross each other no matter
what the value of
q
as seen in the Figure (2) below. One can also show that the shaded
areas (here

is fractional) in the diagram correspond to the values of

, a and q
which
permit stable oscillations to occur for the x coordinate. The
1
( ), ( )
r r
a q b q
+
curves form the
boundaries between the stable and unstable regions.
Figure (2)
The regions of the
, a q
(stability) plane, which correspond to simultaneous stability for
both the x, and the y coordinates are shown as the shaded areas in the Figure (3) below.
Figure (3)
In the diagram
Figure (4), we have
enlarged and colored
pink the first stable
region i.e. the
section of the
, a q

plane, which
corresponds to
simultaneously
stability of the x, and
the y coordinates.
Figure (4)
The value of
q
which corresponds to the maximum value of
0 1
, and a b
in the pink area
is
q
max
0.701
. This is determined by finding the point at which the
0 1
, and a b

curves cross. The value of either ( )
0 1
0.701 , or (0.701) a b
at this point is 0.24276.
The Mass Filter
In order to discuss the mass filtering ability of the quadrupole apparatus we will
consider the top part of the first stability region in the diagram above (i.e. the top part of
the pink area). This expanded view is displayed in the Figure (5). In addition, we note
that the ratio of
/ 2 / a q U V
. A line called the control line or the operating line
shown in the diagram is the straight line
/ a q const
, (here 1/ 3 ; const ). Note that this
line passes through the origin and cuts through the upper portion of the pink area. This
cutting of the
0 1
, a b
curves defines a range of
q
values that the system takes on as it
moves along the control line. This set of
q
values corresponds to a collection of stable
trajectories for the charged particle.
Figure (5)
[Notice that the

values for the x coordinate and y coordinates are in the range

0 1 < <
within the triangular (stable) area.]
Since movement along the
/ a q const
line can be physically accomplished by varying
V along the line
( / 2) U const V
, the system can occupy a series of states, which allow
the particle to pass through the apparatus and be detected. These states will be described
below.
We begin this discussion of mass selection by stating that in a given experiment,
0
and r
are assumed to be fixed. Solving Eqs. (2.1) for V and U along a stability
boundary we get
2 2
0
2 2
0
,
8
( ).
4
r m
V q
e
r m
U a q
e

,
_

,
Eq. (3)
We see that for a given mass to charge ratio, the
( ), a q
versus
q
stability boundary of the
first stable region can be mapped onto the
, V U
plane as shown in Figure (6) below. This
has been done for 3 different mass to charge ratios, all three curves having been
displayed on the diagram below.
Figure (6)
Given the control line shown in the diagram, we see that species which have mass to
charge ratios of 28, 69 and 219 respectively, will pass through the quadrupole and be
detected as V increases along the line. In the first case, masses around 28 will pass if V
is in the range of 37 to 68 volts. In the second case, masses around 69 will pass if V is in
the range100 to 137 volts, and masses around 219 will pass if V is in the range 310 to
440 volts. In the figure under the one given above, we see that the line width of the
change current intensity versus time ( m V t i.e. the RF voltage is varied linearly with
time) is dependent on the width of the line segment cut by the control line across the
stable region. Note also that the line width is proportional to the mass of the particle. If
the slope of the control line is increased, the line width decreases.
A Global View of Stability
Seen in another way, we can think of the m/z (
z e
) curves given above as cross
sections of a surface in
, , U V m
space with the control line being a plane in that space.
We can make this apparent as follows. If we introduce the constant K , which is defined
as
2 2
0
8
r
K
e

,
and the scaled versions of
and V U
defined as
/
/ 2 ,
V K
U K
V = ,
U=
equations (3) take on the forms given in the relations
,
( ).
mq
maq
V =
U
Solving the first of these equations for
q
and substituting this into the second, we get
a U(m,V) =m(V/m),
where it is clear that U is a function of the particles mass m and its scaled RF voltage
V as seen in Figure (7).
Figure (7)
If a control line (here seen as a plane) is passed through this surface we get the plot given
below in Figure(8)
Figure (8)

If now cross sections of the plot in Figure (7) are displayed in the figures below, we get a
series of plots.
In the first case, a plot of U vs. V for various values of the mass is given below in
Figure (9).
Figure (9)
We can see that the position of the maxima move to the right as the mass increases and
the height of the max points also increases with the mass. In fact, one can easily show
that max
V
and max
U
are proportional to the particle mass i.e.
0.7060m
max
V

0.23698m
max
U
. The ratio of these two values determines the slope of the control line,
which passes through the origin, and the tips of each of the curves.
Figure (10)
That is, 0.33567 U = V is the equation of the control curve, which passes through the tips
of all of the mass curves cf. Figure (10). A scaled RF voltage
( 1) m
max
V
corresponding
to the location of the peak in the m1 curve and with constant voltage
( 1) m
max
U
will
uniquely pass a particle with that value of the mass and no other, at those values of the
two voltages.
In another cross section of the surface shown in Figure (11) we plot U vs. m for various
values of V .
Figure (11)
One can see that the control plane (here seen as a horizontal line corresponding to the
value of
1
V =V
) intersects theU versus m curve. That is to say, for a given V there is a
range of masses that will be permitted to pass through the quadrupole apparatus.
In order to narrow down the uncertainty in the mass; it is the usual custom for quadrupole
mass spectrometers to be operated with a control line of high slope as shown in
Figures (5) or (10). That is, the control line is chosen so that it cuts across the tip of the
vs. U V
curves, thereby allowing for high resolution of the mass spectrum.
In general its really not possible to pick a control line that is linear and also just cut
through the tip of the
vs. U V
curves. This is due to imperfections in the fields and the
use of round rods rather than hyperbolically shaped ones. In modern instruments, an
ideal curve scan function of
vs. U V
is used instead of a straight line. This can be seen
in Figure (12) below.
Figure (12)
References
Dawson, P. H. Quadrupole Mass Spectrometry and its Applications, Elsevier Press,
Amsterdam, 1976. Also see a later edition of this text published by the American
Institute of Physics in 1995.
McLachlan, N. W. Theory and Application of Mathieu Functions, Dover Publications,
1964.
Appendix A
Notation
The symbol for the Laplacian operator
2
in two dimensions has the usual meaning i.e.
2 2
2
2 2
x y

+

.
Similarly, the gradient vector operator is defined by
x y z

+ +

i j k
r r r
,
where i, j, k
r r r
are the unit vectors pointing along the x, y, and z-axes respectively.
Formulae for the First Few Eigenvalues and Eigenfunctions of the Mathieu
Equation (
1 q<
)
2 4 6 8
0
1
2
7 29 68687
128 2304 18874368
a q q q q + + +L
2 3
0
1
32
1 1
cos(2 )
2 128
1
cos(4 ) cos(6 ) 7cos(2 )
9
( ) 1 q q q ce +
_
+

,
L
2 3 4 5 6 7 8
1
1 1 1 49 55 265
8 64 1536 589824 9437184 113246208
11
36864
1 b q q q q q q q q + + +L
( )
2
1
1 1 1
sin( ) sin(3 ) sin(3 ) sin(5 )
8 64 3
( ) q q se + + L
Appendix B
In the figures above we have plotted the electrical potential
( , ) x y
at two different
times. That is to say the surface oscillates in time between these two shapes. Note that the
surface contains a saddle point. One can see that if a particle were near the saddle point
and if the surface oscillated at just the right frequency it might be trapped i.e. execute
stable motion within a small region near the saddle point. If on the other hand it did not
oscillate at the correct frequency it would slide off the surface towards infinity. That is to
say, the motion would not be stable in time. This is the physical basis of the quadrupole
mass spectrometer.
The actual path of the changed particle through the mass spectrometer for a stable motion
is pictured below.
In a similar way, the path of a charged particle with unstable motion is show as spiraling
out of control.