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The Gaussian-Lorentzian Sum, Product, and Convolution (Voigt)

Functions Used in Peak Fitting XPS Narrow Scans, and an Introduction to
the Impulse Function

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The Gaussian-Lorentzian Sum, Product,

and Convolution (Voigt) Functions
Used in Peak Fitting XPS Narrow Scans,
and an Introduction to the
Impulse Function

I
n this column I’ll be talking about a nearly unavoidable, and
certainly indispensible, part of X-ray photoelectron spec-
troscopy (XPS): peak fitting of narrow scans. Sherwood
aptly observed that peak fitting in XPS is commonly practiced
because forms of the same element in different oxidation states1
often yield signals that are separated by about as much as their
line widths.1-2 Crist has observed that important decisions in the
laboratory and in industry are regularly based on the results from
peak fitting.3 I have found all of this to be true. The most widely
used functions for fitting peaks in XPS narrow scans are based on
Gaussian and Lorentzian functions, and three such functions are
regularly considered for this purpose: the Voigt function, which
is the convolution of a Gaussian function with a Lorentzian func-
tion (we considered convolution in the last column4), the Gauss-
ian-Lorentzian sum function (GLS), and the Gaussian-Lorent-
zian product (GLP) function. We’ll discuss these three functions
in this article, and then move on to the impulse function, which
I believe is an interesting piece of mathematics that any scientist
or engineer should be familiar with.
XPS Peak Fitting with Voigt and Gaussian-Lorentzian
Sum and Product Functions
In peak fitting an XPS narrow scan, one generally selects a
baseline first followed by a series of peaks, where each peak will,
in general, represent a single chemical state (oxidation state1) of
an element. The most common functions chosen to represent
symmetric XPS signals are the Voigt function, which is the con-
volution of a Gaussian function with a Lorentzian function, the

Figure 1. Graph of the Gaussian function in Equation 1 with parame- Figure 2. Graph of the Lorentzian function in Equation 2 with param-
ters h = 1, E = 0, and F = 1. eters h = 1, E = 0, and F = 1.

2 vtc@vtcmag.com July 2014sVacuum Technology & Coating

Gaussian-Lorentzian sum function (GLS), and the Gaussian-Lo- One can think of at least some of these broadening mechanisms
rentzian product (GLP) function. We’ll discuss these functions as being convolutions of the natural, Lorentzian, line shape with
here. other functions. In mathematics there is a rather amazing theo-
Gaussian and Lorentzian functions play an important role in rem called the Central Limit Theorem. This theorem states that if
science. Their general mathematical forms are given in Equa- you repeatedly convolve a function with itself, or if you convolve
tions 1 and 2, respectively. The general forms of these functions, a series of functions together, the resulting function will general-
including their sum and product functions, have previously ap- ly tend to become more and more Gaussian like.
peared a number of times in the literature.5 We’ll show the plausibility of the Central Limit Theorem here.
Figure 3 shows an example of the slit function, S(x), that we
(x-E) 2
(1) G(x;F, E, h) = h * exp – 4ln2 defined in our previous article (see Equation 3).4 Recall that it
F2
can be viewed as the product of two unit step functions: (x) (see
Equation 4). In particular, Figure 3 shows a slit function with a
h width of one (a = ½) produced by multiplying (½ - x) by (x +
1+4 (x-E)
2
(2) L(x;F, E, h) = ½) (see Equation 5).
F2
(3) S(x) = 1 for x a
These functions are graphed in Figure 1 (the Gaussian) and 0 for x > a
Figure 2 (the Lorentzian) with the following parameters: h = 1
(the functions are given here a height of one), E = 0 (the func-
(4) UnitStep(x) = (x) = 1 for x 0
tions are centered at the origin), and F = 1 (the functions have a
0 for x < 0
width of one). Obviously, both functions are symmetric about
the y-axis. They also have finite integrals and are localized – they
(5) S(x) = (12 – x) (x + 12 ) = 1 for x 12
do not have large tails or other components that extend out to a a= 1
2 0 for x > 12
significant degree. The Gaussian curve is the classic ‘bell-shaped
curve’. The Lorentzian is a little more peaked, i.e., a little nar-
Now, interestingly, if we convolve S(x) with itself (S(x)*S(x))
rower around its maximum, and it extends out a little more than
we get the triangle function, T(x), that is shown in Figure 4.
the Gaussian on its sides, i.e., the Lorentzian has ‘wings’. Any
For those of you that were recently introduced to convolution, it
serious physical scientist should know the difference between
would probably be a good exercise to perform this convolution
these two functions and be comfortable working with them.
to convince yourself that this is true. In any case, I think you’ll
In the theory of X-ray photoelectron spectroscopy, natural line
agree that the triangle function in Figure 4 resembles a Gaussian
shapes are generally assumed to be Lorentzian. However, there
more than the rectangle function in Figure 3. (I admit that T(x)
are many reasons why this natural line shape will not be exactly
is a pretty crude approximation to a Gaussian, but at least it has
observed. There will be some line width to the X-rays that excite
some lines with nonzero slopes…) Notice also that the convolu-
the photoelectrons, e.g., they won’t be perfectly monochromat-
tion of S(x) with itself led to a broader function, which is typical
ic. The photoelectrons then travel through a spectrometer that
of convolution. That is, look at where S(x) in Figure 3 and T(x)
broadens the signal to some degree. The element in question
in Figure 4 have nonzero values, i.e., emerge from the x-axis.
within a sample may be in heterogeneous environment (disorder
Now, to continue this process, let’s convolve T(x) with itself.
broadening), e.g., perhaps the material is a glass. The emission of
(In passing we observe that T(x)*T(x) = S(x)*S(x)*S(x)*S(x),
photoelectrons may also be perturbed by vibrations in the materi-
which is the same as T(x)*S(x)*S(x).) In any case, T(x)*T(x)
al (phonon broadening), where this effect is temperature depen-
yields the function in Figure 5, which is starting to look quite
dent. For a more detailed discussion of these topics, I recommend
Gaussian-like. Notice again that this function is broader than its
the fairly recent book by Briggs and Grant on Surface Analysis.5a

Figure 4. Convolution of the slit function, S(x), with a slit width of 1

Figure 3. Graph of the slit function, S(x), with a slit width of 1. in Equation 5, with itself (S(x)*S(x)) forming a triangle function, T(x).

6ACUUM4ECHNOLOGY#OATINGsJuly 2014 www.vactechmag.com or www.vtcmag.com 3


Figure 5. Convolution of the triangle function with itself (T(x)*T(x))
forming a function that appears rather Gaussian-like.
predecessor (see Figure 4). And finally, note that the convolution
of a Gaussian with a second Gaussian is yet an additional Gauss-
ian, which will be broader than either of the original Gaussians.
So all of this is to show the reasonableness of stating that when
a set of photoelectrons, which may inherently have a Lorent-
zian line shape, is excited by X-rays that have some line width
and shape, and also perturbed by both a spectrometer and the
broadening mechanisms discussed above, we would expect the
resulting signal to have at least some Gaussian character. Thus,
it is common for the components of XPS narrow scans, espe-
cially when monochromatic sources are used, to be modeled as
peaks with both Gaussian and Lorentzian character. The amount
of Gaussian or Lorentzian character assigned to these peaks de-
pends on the factors mentioned above. For example, it has been
recommended that the C 1s signals from polymers be modeled
as 100% Gaussians or 90:10 Gaussian:Lorentzian mixes.3 This
seems reasonable. Polymers will often be in rather heteroge-
neous environments – polymer chains can often be approximat-
ed as random coils.
So we have established that many of the component peaks of
XPS narrow scans will be best defined/fit by peaks that have both
Gaussian and Lorentzian character. The ‘purest’ way to handle
this problem is to use a Voigt function, which is the convolution
Figure 6. Graph of the GLS function (Equation 6) with parameters h =
1, E = 0, and F = 1 for m = 0 (bottom, blue line), m = 0.5 (middle, red
line), and m = 1 (top, yellow line).
4 vtc@vtcmag.com
of a Gaussian and a Lorentzian. As discussed in our previous ar-
ticle,4 the only problem with this approach is its complexity – the
necessary convolution is computationally expensive. According-
ly, two simpler functions have been widely used as surrogates
for the Voigt function. These are the Gaussian-Lorentzian sum
(GLS) and Gaussian-Lorentzian product (GLP) functions. The
GLS function has the following form:
h*m
(6)GLS(x;F,E,m,h)=h*(1– m)exp –4ln2 (x-E)
2
+
(x–E)2
2
F 1+4
F2
Notice that the first and second terms in this function are the
Gaussian and Lorentzian functions in Equations 1 and 2, weight-
ed by a mixing parameter, m. That is, for m = 0, Equation 6
reduces to Equation 1, a Gaussian, and for m = 1, Equation 6 re-
duces to Equation 2, a Lorentzian. Obviously, by varying m from
0 to 1 we obtain a series of functions that have more Gaussian or
more Lorentzian character. It should also be clear that m could be
a fitting parameter in an algorithm used to fit XPS narrow scans.
Figure 6 shows the GLS function (Equation 6) for three values
of m: m = 0 (the blue line), which again is a Gaussian, m = 1 (the
green line), which is again a Lorentzian, and m = 0.5 (the red
line), which runs more or less between the other two functions.
Figure 7 goes a little further, zooming in on the region where the
Gaussian and Lorentzian functions differ most for m = 0, 0.1,
0.3, 0.5, 0.7, and 1. It is clear that the GLS function varies in a
reasonable way between a pure Gaussian and a pure Lorentzian
function.
Now let’s compare the GLS function to the GLP function.
This latter function is defined in Equation 7. Clearly, from its
name, we expect that we will be dealing with the product of a
Gaussian function and a Lorentzian function, which is indeed
the case. That is, m = 0 in Equation 7 results in a pure Gaussian
(Equation 1), and m = 1 in Equation 7 yields a pure Lorentzian
(Equation 2).
(7) GLP(x;F,E,m,h) = h * exp – 4ln2(1-m) (x-E)
2
1
*
2
F (x-E)2
1+4m
F2
Figure 7. Graph of the GLS function (Equation 6) with parameters h
= 1, E = 0, and F = 1 for (from bottom to top) m = 0, 0.1, 0.3, 0.5, 0.7,
and 1.
July 2014sVacuum Technology & Coating
Figure 8. Graph of the GLP function (Equation 7) with parameters h =
1, E = 0, and F = 1 for m = 0 (bottom, blue line), m = 0.5 (middle, red
line), and m = 1 (top, yellow line).
So all of this sounds pretty good, and one might think at this
point that the GLS and GLP functions would be more or less
interchangeable. I you believe this, you may wish to continue
reading. Figure 8 shows the GLP function for m = 0, m = 0.5,
and m = 1. It is obvious here that while the m = 0.5 GLS func-
tion was approximately in the middle of the pure Gaussian and
Lorentzian functions (see Figure 6), the m = 0.5 GLP function is
only slightly different from the pure Gaussian function. Things
just don’t look right here, which causes one to ask the question:
Why would the m = 0.5 GLP function not look more like the m
= 0.5 GLS function? Here’s the answer. Notice that the Gaussian
function is rather well contained and goes to zero quite quickly.
As a result, when one multiplies a Lorentzian by a Gaussian, the
‘wings’ of the Lorentzian are multiplied by values that are pretty
close to zero and as a result they essentially disappear. Figure 9
further illustrates this issue. It shows a zoom in view of the m =
0.5 GLP function and also of the m = 0.9 GLP function. Here,
the graph of the m = 0.9 GLP function reconfirms that the GLP
function is a less than ideal representation of something interme-
diate between a pure Gaussian and a pure Lorentzian function,
i.e., we’d expect that the m = 0.9 GLP function would not be sig-
nificantly different from a pure Lorentzian, but the m = 0.9 GLP
function in Figure 9 only extends about half way between the
pure Gaussian and Lorentzian functions, and it does not appear
to effectively represent the ‘tails’ of the Lorentzian.
Around 1980,6 the GLP function was recommended in the
literature for XPS narrow scan peak fitting. This suggestion ap-
pears to have been relatively influential. However, a more recent
paper in 2007 by Hesse, Streubel, and Szargan5c was unable
to verify the previous recommendation – in their analyses the
GLS performed better than the GLP. Their study also had a rath-
er pragmatic component it. They looked at the fitting functions
(Voigt, GLS, and GLP) that are available in different XPS soft-
ware packages. Unfortunately, not all of the functions are avail-
able in all of the programs, and one software package only had
the GLP as an option. One must sometimes do the best one can
with the tools available. Hesse and coworkers also plotted the
GLS with m = 0.5, the GLP with m = 0.5, and a Voigt function
6ACUUM4ECHNOLOGY#OATINGsJuly 2014 www.vactechmag.com or www.vtcmag.com
Figure 9. Graph of the GLP function (Equation 7) with parameters h =
1, E = 0, and F = 1 for, going from bottom to top, m = 0 (blue line), m =
0.5 (red line), m = 0.9 (yellow line), and m = 1 (green line).
made by convolving Gaussian and a Lorentzian functions with
equal widths. All three of these functions had equal widths of
2. I’ve reproduced this plot in Figure 10, albeit with the peaks
shifted to the origin for consistency with the other peaks in the
other figures shown herein. The Voigt function (yellow line) is
the widest of the three functions. The red line just inside it is
the GLS function. Obviously the GLS function approximates the
Voigt function pretty well. The GLP function is represented by
the blue line. It is less obvious that it is a good approximation to
the Voigt function. I performed a citation search on the Hesse
paper. While a number of groups have cited it as a reference to
their choice of fitting functions for XPS narrow scans, I have not
been able to find a study that contradicts their results or that fur-
ther develops this topic, i.e., I assume here that anyone writing on
the topic would cite the Hesse paper. In 2003, Neal Fairley also
discussed this issue, noting, as did Hesse, the significant decrease
of the Lorentzian’s tail when it is multiplied by a Gaussian.5a In
summary, for the reasons outlined in this article, and also in the
Hesse and Fairley documents, we similarly favor the GLS over
the GLP for peak fitting XPS narrow scans.
Figure 10. Graphs of the GLS function with m = 0.5 (red line), the
GLP function with m = 0.5 (blue line), and the Voigt function (yellow
line). All three functions have widths of 2 and are centered at the origin.
The Voigt function here is the convolution of a Gaussian function with
a width of 1.3 and a Lorentzian function with the same width.
5
The Impulse Function
I wanted to take the rest of the space in this column here to
discuss a function that is closely related to the topics covered
here and in the previous column: the impulse function. I believe
that the ideas behind this function are important for a physical
scientist to understand well. The impulse function shows up
when one studies convolution and also the Fourier transform –
convolution and the Fourier transform are quite closely related.
It is also shows up in surface and materials characterization, e.g.,
it helps one understand Fourier transform infrared spectroscopy
(FTIR), which is a powerful materials characterization method.
I used two examples of the impulse function in my first article
earlier this year – in the description of some FTIR work I did as a
graduate student and as a representation of a sharp AFM tip.7 The
impulse function is also an important topic in physics – it can be Figure 11. Graph of 3 (x + 4).
used to represent point masses and point charges. I would hope tion is centered at the origin. Now to find the limits over which
that my students would be conversant in its mathematics and the this function has a value of unity, we set x/b = ½ and get x = ±
ideas surrounding it. As might be expected, this function goes by b/2, which means that the function has a value of 1 between –b/2
more than one name. Many chemistry students encounter it for and b/2, and the width (base) of the function is b. Now let’s put
the first time when they study quantum mechanics as the ‘Dirac this all together. Convince yourself that 2 ((x+3)/4) is repre-
delta function’ or just the ‘delta function’, (x). We will also rep- sented by the graph in Figure 12, i.e., it is a rectangle function
resent the impulse function as (x) in this article. that is centered at x = -3 with a height of 2 and a width of 4.
The impulse function belongs to an unusual class of functions There are a number of mathematical definitions for the im-
that exist only in a limit, and our description of it will begin with pulse function. We’ll focus here on one of the more standard and
the definition of a function that we will call the rectangle func- simple definitions of it. For many purposes this definition is per-
tion: (x).8 (x) is quite similar to the ‘slit’ function defined in fectly adequate, although if you need to differentiate the impulse
Equation 3, but it will be, perhaps, easier for us to work with as function, and sometimes this is necessary, you will probably
we try to understand (x). (x) is defined as follows: want to choose a different definition, e.g., an impulse function

!
0 for x >½ defined through a triangle function or a Gaussian function. For
(8) (x) = ½ for x = ½ most practical purposes, however, the definition of the impulse
1 for x <½ function does not matter. It can’t! The idea behind the impulse
function is that it becomes so narrow that it does not matter
Figure 3 is again a good representation of this function – con- which definition we choose! (We get the same answer from any
vince yourself that this is the case. Now, let’s see how we can representation of it.) We will begin by defining the impulse func-
manipulate (x). First, we can change its height by multiplying tion at the origin, but we will relax this constraint shortly and
it by some constant, h. That is, h (x) has the same definition as show that it can be shifted to any position along the x-axis. The
Equation 8, except that it will have a value of h for x < ½ and h/2 impulse function, (x), is a function that only exists in a limit.
for x = ½. Thus we see that we can easily manipulate the height Accordingly, let’s first consider the function:
of (x). Obviously, we could also multiply (x) by a negative
constant. (9) lim (x/ )
0
We can also shift (x) along the x axis. To do this, we recog-
nize that the center of (x) is where its argument is zero. Accord-
ingly, (x - c) must be a rectangle function that is centered at the
point c along the x-axis, i.e., if you solve x – c = 0, you get x =
c. To find the limits over which (x - c) is equal to one, we can
again go back to its definition in Equation 8 and set the argument
equal to x = ½. Thus, if x – c = ½ for (x - c), the limits over
which this function has a value of 1 are c ± ½. Thus, the function
3 (x + 4) should have a height of 3, be centered at the point x
= -4, and have a value of 1 between x = -4.5 and -3.5. Convince
yourself that this is the case and that this function is correctly
represented in Figure 11.
But there’s more. We can also change the width of this func-
tion. To do this, let’s consider the function (x/b), where b is a
constant. First, to find it’s center point, we again set its argument
equal to zero and solve for x: x/b = 0, x = 0. Obviously the func- Figure 12. Graph of 2 ((x+3)/4).

6 vtc@vtcmag.com July 2014sVacuum Technology & Coating

Clearly this is a rectangle function that is centered at the origin
with width of . The area of this function is also , i.e., as 0,
the area of the function goes to 0. Before moving on, you should
convince yourself that these statements are true. Now, let’s mul-
tiply this function by 1/ to get one of the definitions of the im-
pulse function, (x):
(10) (x) = lim 1 (x/ )
0

So now we have a function, (x), that has a height of 1/ and

a width of . This means that the area of (x) stays constant at
one: *1/ = 1. (I’ll use the asterisk symbol here, *, to mean mul-
tiplication, which is common in many computer programming
languages. Unfortunately, it is also used to denote convolution
and we will also use it in this way in this article. You should be
Figure 14. Graphs of x2 + 2x + 3 (blue line), (x)(red line), and 3 (x)
able to figure out how it is being used by its context.) Thus, if we
(green line).
take 0, (x) becomes infinitely narrow and infinitely high
while maintaining a constant area of one. Figure 13 shows a plot the red line in Figure 14), multiplying it by f(x) = x2 + 2x + 3 (the
of (x) (blue line), (1/2)
1
(x/21) = 2 (2x) (red line), and (1/4)
1
(x/41) blue line in Figure 14) as follows:
= 4 (4x) (green line). This figure shows us how as 0, (x)
gets higher and narrower, while keeping its area constant. Thus, (14) –
(x)(x2+ 2x+3) dx
we note that (x) can be defined as follows: To solve Equation 14, we recognize that the (x) function is
zero everywhere except between limits of -0.5 and +0.5. Of
(11) !
(x) = 0 for x 0
for x =1 course this means that the product of (x) and x2+ 2x+3 is also
and zero everywhere except between these two values. Thus, with-
out changing the value of Equation 14, we can change its limits
(12) –
(x) dx = 1 as follows:
Note that Equations 11 and 12 do not restrict the definition of (14) (x)(x2+ 2x+3) dx = 0.5
(x)(x2+ 2x+3) dx
– –0.5
(x) to Equation 10, although Equation 10 clearly meets the defi-
nition of the impulse function created by Equations 11 and 12. We next recognize that (x) has a value of unity over these lim-
Now let’s consider one of the important properties of (x), its, so again without changing our final answer in any way we
which is how it behaves in an integral. In particular, let’s consid- can simplify Equation 14 to:
er the integral:
(15) 0.5
–0.5
(x2+ 2x+3) dx
(13) –
(x)f(x) dx
To understand what (x) is doing in Equation 13, we will take Equation 15 is a very simple, definite integral that upon evalua-
the three increasingly narrow approximations of (x) shown in tion yields 3.0833.
Figure 13 and see how they interact with x2 + 2x + 3, which will But we could also make an approximation here. (When I was
play the role of f(x) in Equation 13. We will start with the broad- taking classes in the Materials Science department at Stanford
est of the three approximations to (x) in Figure 13: (x) (now I recall one professor would say: “You can’t do good science
without making good approximations”. Another quote I heard
more than once during this time was: “A good scientist is skep-
tical, but not cynical.” This second quote doesn’t have much to
do with this article, but I think it’s a good piece of advice.) So
even though Equation 15 can be solved simply and explicitly,
we’ll make an approximation, where this exercise will again help
us understand what is going on with the impulse function. We
will approximate the function f(x)= x2 + 2x+3 by the value of the
function at the center of the (x) function, i.e., at x = 0, which
gives us f(0) = 3. That is, we will assume that from -0.5 to 0.5, x2
+ 2x+3 has a value of 3. This is the green line in Figure 14. So
now, to approximate Equation 15, we multiply the height of the
(x) function (unity) by the approximation to the x2+ 2x+3 func-
tion (3) over the same range to get a line at y = 3 (also the green
line in Figure 14). We then multiply this height by the width of
Figure 13. Graphs of of (x) (blue line), (1/2)
1
(x/ 12)=2 (2x)(red line),
and (1/4)
1
(x/41) = 4 (4x) (green line). the rectangle – the region over which the product of the functions

6ACUUM4ECHNOLOGY#OATINGsJuly 2014 www.vactechmag.com or www.vtcmag.com 7

 1
Figure 15. Graphs of x2 + 2x + 3 (blue line), (1/2) (x/ 12) = 2 (2x) (red
line), the approximation to x2 + 2x + 3 (y = 3 from -0.25 to 0.25, yellow
line), and the product of 2 (2x) and 3: 6 (2x) (green line).
is not zero, i.e., from -0.5 to 0.5, which is 1. Accordingly, 1*1*3
= 3. That is, we have just approximated our integral as the area
under the green line in Figure 14. Compared to the true value of
the integral (3.0833), this isn’t such a bad approximation.
Let’s continue the process. We’ll now take the next approxi-
mation of the impulse function in Figure 13, multiply it by x2 +
2x+3, and take the integral of the product of the two functions,
as follows:
(16) 1
x/ 12 (x2+ 2x+3) dx
– (1/2)
Of course our approximation to the impulse function is better
here – it is narrower and taller than in the previous example. Let’s
do a similar analysis to the one we did before. The function (1/2) 1
x/ 21 (red line in Figure 15) is only nonzero from -0.25 to
0.25, so we will make these values our limits of integration. We
recognize that x/ 12 has a value of unity over these limits, and
so we get:
(17) 2 –0.25
0.25
(x2+ 2x+3) dx
This definite integral has a value of: 3.0208. But we can again
approximate the x2+ 2x+3 function (blue line) by its value at the
center of the (1/2)
1
x/ 12 rectangle function, i.e., at x = 0, which
again gives us f(0) = 3 (yellow line in Figure 15). Thus, the ap-
proximation of the integral (Equation 16) is the value of the prod-
uct of the two functions: 3*2 (the yellow and red lines in Figure
15, which gives the green line), multiplied by the width of the
function: ½. That is, the approximation to the area in Equation
16 is 3*2*½ = 3. Notice that this approximation is the same as it
was before, which is not a coincidence, and that we are now even
closer to the true value of the integral (3.0208).
We’ll repeat the process for the third, and narrowest, approxi-
mation of the impulse function in Figure 13: (1/4)
1
(x/41) = 4 (4x)
(the red line in Figure 16). Accordingly, we’ll multiply it by x2+
2x+3 and take the integral of the product of the two functions:
(18) 1
(x/41) (x2+ 2x+3) dx
– (1/4)
The 1
(x/ 41) rectangle function is only nonzero from -0.125
(1/4)
8 vtc@vtcmag.com
Figure 16. Graphs of x2 + 2x + 3 (blue line), (1/4)
1
(x/41) = 4 (4x)(red
line), the approximation to x2 + 2x + 3 (y = 3 from -0.25 to 0.25, yellow
line), and the product of 4 (4x) and 3: 12 (4x) (green line).
to 0.125, it is unity within these limits, and we again do a little
algebra to get:
(19) 4 0.125
–0.125
(x2+ 2x+3) dx
This integral evaluates to 3.0052. Again, our approximation to
this integral is given by the value of the rectangle function over
the limits of integration: 4 (red line in Figure 16), multipled by
the approximation of the function x2+ 2x+3 at x = 0, i.e., f(0) = 3
(yellow line in Figure 16), which gives the green line in Figure
16. We now multiply this height (12) by the width of the function
(1/4) to give us the value of the approximated integral: 12/4 = 3.
We are now even closer to the true value of the integral (3.0052)
than we were before.
What if we continue the process, allowing the rectangle func-
tion to become infinitely narrow and infinitely high while keep-
ing its area at unity? That is, the width of the rectangle function,
, goes to zero because 0, while the height of the function
1/ goes to infinity as 0. In each case, we approximate the
integral in Equation 13 by multiplying 1/ by by f(0), which
is what we just did for the three functions in Figure 13 that we
applied to a simple polynomial. Thus, Equation 13 reduces to *
1/ * f(0) = f(0). Clearly, this approximation becomes perfect in
the limit of 0. Mathematically, we write:
(20) (x) f (x) dx = f (0)
–
This result is an example of the sifting property of the impulse
function.
As one might expect, the impulse function can be shifted to
any point along the x-axis. That is, (a - x) is an impulse function
centered at the point a on the x-axis. In other words, because
the impulse function is only nonzero when its argument is zero,
we solve a – x = 0 to get x = a. Clearly then, if we integrate the
product of (a - x) and f(x), we will pick out the value of f(x) at
the point where x = a, i.e., we will get back f(a):
(21) –
(a–x) f (x) dx = f (a)
Thus we can pull out any value of a function by using an appro-
priately shifted impulse function.
July 2014sVacuum Technology & Coating
 In our last column we talked about convolution,4 where this
important mathematical operation is defined by:
(22) f(x) * g(x) = f (u) g (x–u) du = g (u) f (x–u) du
– –
Now, what happens when one of these functions is the impulse
function? Let’s start by putting f(x) = (x) into Equation 22 to
give us Equation 23:
(23) (x) * g(x) = –
(u)g(x–u) du = –
g(u) (x–u) du
Let’s evaluate the middle part of this equation: – (u)g(x–u)du.
Obviously (u) is zero everywhere except where u = 0. Thus,
we pick out the value of g(x-u) where u = 0, which gives us:
(u)g(x–u)du = g(x). In the evaluation of the second integral:
– 2014.
–
g(u) (x–u)du, we note that ‘x’ is playing the role of a constant
in this integral, which was also the case for the first integral.
Thus, (x–u), which is an impulse function that is shifted to the
point x on the x-axis, will pick out the value of g(u) where u =
x, i.e., – g(u) (x–u)du = g(x). As expected, we get the same
answer either way. This exercise leads us to the conclusion that
the convolution of any function with a delta function is the func-
tion itself:
(24) (x) * g(x) = g(x)
At this point, it should be clear what we meant in our first col-
umn7 when we noted that the interaction of an extremely sharp
atomic force microscopy (AFM) tip with a surface can be mod-
eled as the convolution of an impulse function with a function
that represents the surface topology. In other words, we can see
mathematically why an infinitely narrow AFM tip will best map
out surface topography.
Conclusion
We have covered two topics that I think can be summarized
as follows. First, as far as I can tell, the GLS function seems to
make more sense as a surrogate for the Voigt function than the
GLP function in XPS peak fitting. Other recent reports seem to
agree with this recommendation. Second, the impulse function
shows up in many places in science and is worth understanding.
It has some interesting properties. It picks out specific values of
functions in integrals and the convolution of a function with the
impulse function yields that same function.
References
1. Gupta, V.; Ganegoda, H.; Engelhard, M. H.; Terry, J.; Linford, M. R.,
Assigning Oxidation States to Organic Compounds via Predictions
from X-ray Photoelectron Spectroscopy: A Discussion of Approach-
es and Recommended Improvements. J. Chem. Ed. 2014, 91 (2),
232–238.
2. Sherwood, P. M. A., Curve fitting in surface analysis and the effect
of background inclusion in the fitting process. J. Vac. Sci. Technol. A
1996, 14 (3), 1424 - 1432.
3. Crist, B. V., Advanced Peak-Fitting of Monochromatic XPS Spectra.
Journal of Surface Analysis 1998, 4 (3), 428 - 433.
4. Linford, M. R., An Introduction to Convolution with a Few Com-
ments Beforehand on XPS. Vacuum Technology & Coating June,
5. (a) Fairley, N. Surface Analysis by Auger and X-ray Photoelectron
Spectroscopy. Eds.: Briggs, D. and Grant, J.T., IM Publications:
2003; (b) CasaXPS, Peak Fitting in XPS. Casa Software Ltd. (http://
www.casaxps.com) 2006; (c) Hesse, R.; Streubel, P.; Szargan, R.,
Product or sum: comparative tests of Voigt, and product or sum of
Gaussian and Lorentzian functions in the fitting of synthetic Voi-
gt-based X-ray photoelectron spectra. SURFACE AND INTERFACE
ANALYSIS 2007, 39, 381–391.
6. (a) Sherwood, P. M. A., Practical Surface Analysis. Eds.: Briggs,
D. and Seah, M.P., John Wiley: Chichester, 1983; (b) Ansell, R. O.;
Dickinson, T.; Povey, A. F.; Sherwood, P. M. A., X-ray photoelectron
spectroscopic studies of electrode surfaces using a new controlled
transfer technique. Part II. Results for a molybdenum electrode and
the curve fitting procedure. J. Electroanal. Chem. 1979, 98, 79 - 89.
7. Linford, M. R., Introduction to Surface and Material Analysis and
to Various Analytical Techniques. Vacuum Technology & Coating
February, 2014.
8. Bracewell, R. N., The Fourier Transform and its Applications. Mc-
Graw-Hill: 2000.

Acknowledgement and Contact Information

All of the calculations and corresponding figures in this col-
umn were made with Wolfram Mathematica 9.0. I thank and ac-
knowledge the organizations and individuals that have allowed
me to use their content in this and previous articles. However,
I would be happy to consider information from any reputable
source – if any readers or representatives of companies wish
to contact me, I can be reached at surface.materials.analysis@
gmail.com. I can also be contacted through Research Gate under
my full name: Matthew R. Linford. I also thank Vincent Crist
for reading this article before it went to press and for discussing
it with me.

6ACUUM4ECHNOLOGY#OATINGsJuly 2014 www.vactechmag.com or www.vtcmag.com 9

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