TIME-OF-FLIGHT MASS SPECTROMETRY: INTRODUCTION TO
THE BASICS
https://onlinelibrary.wiley.com/doi/epdf/10.1002/mas.21520
Ulrich Boesl*
Department of Chemistry, Physical Chemistry, Technische Universit€at
M€unchen, Garching, Germany
Received 8 June 2016; revised 2 August 2016; accepted 19 August 2016
Published online 9 November 2016 in Wiley Online Library (wileyonlinelibrary.com). DOI 10.1002/mas.21520
The intention of this tutorial is to introduce into the basic
concepts of time-of-flight mass spectrometry, beginning with the
most simple single-stage ion source with linear field-free drift
region and continuing with two-stage ion sources combined with
field-free drift regions and ion reflectors—the so-called reflec-
trons. Basic formulas are presented and discussed with the focus
on understanding the physical relations of geometric and
electric parameters, initial distribution of ionic parameters, ion
flight times, and ion flight time incertitude. This tutorial is aimed
to help the applicant to identify sources of flight time broadening
which limit good mass resolution and sources of ion losses which
limit sensitivity; it is aimed to stimulate creativity for new
experimental approaches by discussing a choice of instrumental
options and to encourage those who toy with the idea to build an
own time-of-flight mass spectrometer. Large parts of mathemat-
ics are shifted into a separate chapter in order not to overburden
the text with too many mathematical deviations. Rather, thumb-
rule formulas are supplied for first estimations of geometry and
potentials when designing a home-built instrument, planning
experiments, or searching for sources of flight time broadening.
# 2016 Wiley Periodicals, Inc. Mass Spec Rev 36:86–109, 2017.
Keywords: two-stage ion source; space focus; ion reflector;
reflectrons; laser mass spectrometry; experimental options of
ToF-MS
I. INTRODUCTION
“A pulsed mass spectrometer with time dispersion” published in
1946 (Stephens, 1946) may be considered the beginning of time-
of-flight mass spectrometry (ToF-MS). The early ToF-instru-
ments revealed a mass resolution which just allowed the
separation of mass 20 and 21. In 1955, space focus and delayed
ion extraction have been introduced (Wiley & McLaren, 1955).
The former measure helped to compensate for initial spatial
distributions, the latter for initial velocity distributions of ions
formed in the ToF ion source. A mass resolution of 500 was
reached. A further step forward in mass resolution brought the
invention of Mamyrin in 1966 (Mamyrin, 1966; Mamyrin et al.,
1973). He extended ToF-instruments by an ion reflector and
achieved mass resolutions of 3,000. But it was not until the

Correspondence to: Ulrich Boesl, Department of Chemistry, Physical
Chemistry, Technische Universit€at M€unchen, Lichtenbergstr. 2, 85748
Garching, Germany.
E-mail: ulrich.boesl@tum.de
Mass Spectrometry Reviews 2017, 36, 86–109
# 2016 by Wiley Periodicals, Inc.
1990s that ToF-MS gained significant interest. In this time, ToF-
MS was of fundamental importance for the Nobel prizes in
chemistry to Curl, Kroto, and Smalley in 1996, to Zewail in
1999, and to Tanaka in 2002, awarded for the detection of
fullerenes (Curl & Smalley 1988), the studies of chemical
reactions by femtosecond spectroscopy (Pedersen, Herek, &
Zewail, 1994), and the extension of mass spectrometry to large
molecules by matrix-assisted laser desorption ionization
(MALDI) (Karas & Hillenkamp, 1988; Tanaka et al., 1988;
Bahr, Karas, & Hillenkamp, 1994).
It was the availability of fast electronics, data acquisition,
and data processing on the one hand side and of pulsed
ionization sources on the other which finally pushed ToF-MS to
become one of the top mass spectrometric techniques. Besides
other pulsed ionization methods, such as SIMS (secondary
ionization mass spectrometry) (Benninghoven & Sichtermann,
1978), in particular ionization with pulsed laser light was
responsible for this success. Pulsed lasers were applied in gas
phase as well as in solid phase ionization. In the former case,
they allowed for mass selective molecular spectroscopy (Boesl,
1991, 1999) and highly selective ionization (Boesl, 2000). In
the latter case, they were used to desorb and ionize large
biomolecules in one single excitation step (Karas & Hillenkamp,
1988; Tanaka et al., 1988). In the meanwhile, application fields
of ToF-MS reach from high precision nuclear physics (Plaß
et al., 2007; Wolf et al., 2013), where new isotopes are
investigated in multi-reflection-reflectrons, to extraterrestial
chemical analysis, where reflectron-ToF instruments in space
crafts serve to detect organic precursors of life (Kissel &
Krueger, 1987) or traces of early history of the sun system
(Balsiger et al., 1998; see also http://sci.esa.int/rosetta/54086-
rosina); they reach from fundamental molecular research, where
molecular transition states as intermediate steps of chemical
reactions are investigated (Metz et al., 1990), to analytical
chemistry of air pollutants (Boesl et al., 2000) and sequence
analysis of DNA (Gut, 2004).
The main features which made ToF-MS so favored is the
combination of

fairly high mass resolution;

a mass scale which theoretically is not limited to large
masses;

high compatibility with other techniques of selection; and

reasonably easy way of design, mounting, and handling.
In particular, the latter feature is the reason why in many
research labs home-built ToF-instruments are used with great
success.
 TIME-OF-FLIGHT MASS SPECTROMETRY &

In this tutorial, basic concepts and formulas of ToF-MS are A. Flight Time in the Acceleration Region
presented and discussed. Although there exist excellent pro-
The acceleration b in a homogeneous electric field Ea is constant
grams (an example is the program Simion 2016, see www.
with b ¼ qEA/m. The finally achieved ion kinetic energy is
simion.com) to numerically calculate whole time-of-flight mass
Ekin ¼ Epot(t ¼ 0) ¼ qU ¼ xAqEA. The time to achieve Ekin is
spectrometers, the understanding of physical relations in ToF-
MS supported by analytical formulas and their discussion is of rffiffiffiffiffi sffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffi
great use. It helps to identify sources of flight time broadening 2x x 2xm m
t¼ ¼2 ¼ ¼ 2x deduced from
ruining good mass resolution and sources of ion losses degrad- b v qEA 2qU
ing sensitivity, to find innovative approaches for new experi-
ments and instrumentations, and last not least to build own time- Zt Zt
1 qEA
of-flight mass analyzers at fairly low cost and optimized for b ¼ const:; v ¼ b dt ¼ bt; x ¼ v dt ¼ bt2 ; b ¼
actual purposes. To leave the view open to fundamental relations 2 m
0 0
of physical parameters and their discussion, large parts of
mathematics are shifted into the Appendix in Section 8. Rather, The time for acceleration in the acceleration region x ¼ xA
thumb-rule formulas are given to achieve first estimations of is then
geometry and potentials when designing a home-built instru-
ment, planning experiments including a time-of-flight analyzer rffiffiffiffiffi rffiffiffiffiffiffi
M pffiffiffiffiffi M
or searching for sources of flight time broadening. tacc ¼ xA 2C ½ms or tacc ¼ xA 2C ½ms ð1Þ
In Sections 1 and 2, ion flight times and sources of ion flight U EA
time broadening of the basic ToF-spectrometer with single-stage
ion source (two electrodes with one electric field) are discussed.
Sections 3 and 4 introduce into two-stage ion sources and ion with mass m ¼ M mu ¼ M  1.67  1027 kg and charge q ¼
reflectors, which form together the so-called reflectron-ToF e ¼ 1.60  1019 As resulting in constant C:
instruments. In Section 5, so-called space-focus conditions of rffiffiffiffiffiffi
mu
two-stage ion sources and two-stage ion reflectors are presented C¼ ¼ 0:71986 ms V 1=2 cm1  0:72 ms V 1=2 cm1
and discussed. They allow for compensation of ion kinetic 2q
energy incertitude caused by primary spatial distribution of ions
at ion formation and by primary velocity distribution due to
B. Flight Time in the Field-Free Drift Region
other effects. In Section 6, other sources of ion flight time
broadening than spatial distribution and measures to reduce their Ion velocity v in the field-free drift region is constant, the ion
influence are discussed. Finally, in Section 7, some options of kinetic energy is 1/2mv2 ¼ qU ¼ q xAEA. Flight q time
ffiffiffiffiffiffiffit in a field-
instrumental and experimental extensions of ToF-instruments qffiffiffiffiffiffiffi
free region then is t ¼ v ¼ x 2qU with v ¼ 2qU
x m
m and with
are described which hopefully stimulate the creativity of
applicants to use their ToF-instrument for further exciting x¼s
experiments. Most citations are given to provide examples or rffiffiffiffiffi rffiffiffiffiffiffi
further information rather than complete reviews of the field. M s M
tdrift ¼s C½ms or tdrift ¼ pffiffiffiffiffi C½ms ð2Þ
For such reviews and further information, see Schlag (1994), U xA EA
Guilhaus (1995), Cotter (1997), Grotemeyer (2001), Wollnik
(2013), Radionova, Filippov, & Derrick (2015). With the distances xA and s in acceleration and drift region
in cm, the molar weight M in atomic mass units and the
II. THE BASIC TIME-OF-FLIGHT MASS acceleration potential U in V. Flight times in Equations (1) and
SPECTROMETER (2) are given in two forms: one as a function of the acceleration
potential U and one as function of the acceleration space xA. The
The most basic ToF-mass analyzer consists of an acceleration latter is needed to determine the dependence of acceleration and
region xA with a homogeneous electric field EA and a field-free flight times on changes of xA and thus the flight time incertitude
drift region s as schematically shown in Figure 1. In the due to initial spatial distribution of ions at their formation in the
following, flight times, incertitudes of flight times, and possibili- ion source.
ties to compensate for the latter are discussed.
C. Ion Flight Time Incertitude Dt
The ion arrival time at the detector is subject to incertitude Dt if
the time and position of ion formation as well as the initial
velocity in direction of ion extraction are not well defined but
exhibit certain initial distributions Dt, Dx, and Dv, respectively.
While Dt caused by Dt and Dx can be directly calculated,
Dt caused by Dv can be approximated by a pseudo-temporal
and a pseudo-spatial part. This approach is quite useful to
understand the effect of an initial velocity distribution (e.g., of
the primary neutral atoms or molecules) and to find appropriate
countermeasures to compensate for these effects. This approach
FIGURE 1. Scheme of the basic ToF-mass analyzer. is illustrated in Figure 2 and explained in the following.

Mass Spectrometry Reviews DOI 10.1002/mas 87

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FIGURE 2. Replacement of initial velocity distribution by an initial spatial and an initial temporal pseudo-
distribution. This describes how initial velocity distribution Dv contributes to the flight time incertitude Dt.
This two-component effect can be illustrated by the
following procedure. Ions starting at identical time at identical
positions but with different initial velocities vi (e.g., v1, v2, v ¼ 0,
v1, v2, as shown in Fig. 2) may be represented by ions with
identical velocities (actually with v ¼ 0), but at different starting
positions Dxi (e.g., Dx1, Dx2, Dx ¼ 0; see Fig. 2) and different
starting times Dti (e.g., t1, t2, t ¼ 0, t1, t2, see Fig. 2). These
pseudo starting conditions Dxi and Dti are correlated with the
starting velocities vi in the following way:
1. Dxi q EA ¼ 1/2 m vi2 ¼ Ui (initial kinetic energy);
2. Dti ¼ 2 Dxi/Dvi (Dti for particles flying “forwards” and
þDti for those flying “backwards”).
Dti and Dxi are chosen in such a way, that primary particles
flying in forward direction (direction of ion extraction) pass the
original position x ¼ 0 at time t ¼ 0, and that primary particles
flying in backward direction pass this original position x ¼ 0
after a turn-around time. In both cases, the ions pass the original
(identical) starting position with their original amount of
velocity |vi|. In the second case, however, the sign of vi has
changed. The turn-around-time of ions starting backwards is
2 Dti with respect of those starting forwards having the same
amount of initial velocity |vi|. Dti is a real temporal incertitude
and is kept constant during the whole ion flight from ion source
to ion detector.
In the following Dti is called turnaround time. It is very
mistakable, that commonly the whole time error 2 Dti is called
turn-around-time. This implicates that ions with primary
velocity in forward direction (not undergoing a turn-around
motion) are not subject to a pseudo-temporal error, which of
course is wrong. A typical case is MALDI, where ions start from
a vertical surface and therefore do not exhibit initial backward
velocities. Nevertheless, also at MALDI a pseudo-temporal
flight time error due to initial velocity distribution has to be
considered. All effects contributing to the total error in ion flight
time are listed in Table 1. Because these effects are of statistical
origin (assumption of a Gaussian distribution) the total error
Dt ¼ (Dtt2 þ Dtx2 þ Dtv2)1/2.
D. Possibilities to Compensate for Initial Distributions
of Dt, Dx, and Dv
An initial Dt can be compensated either by a short ion generation
time such as a short ionizing laser pulse or by generating the
ions for some time in a field-free ion source and then extracting
them simultaneously by applying a pulsed extraction field.
88
In this context, one should not forget about the detector response
time which also is a fixed temporal contribution to the ion flight
time. The effect of an initial spatial distribution of ion formation
can be kept small by weak electric extraction fields which cause
only a small difference of potential energy within Dx. Another
possibility is to position the ion detector surface at the so-called
space focus of the ion source which is discussed below. The
influence of an initial velocity distribution (the velocity compo-
nents in direction of ion extraction count) may be reduced by
keeping this distribution small. If Dv of the primary neutral
atoms or molecules is relevant then its reduction is achieved in a
molecular beam which is oriented perpendicular to the ion
extraction or in a supersonic molecular beam with very uniform
primary velocities. In Table 2, first countermeasures to compen-
sate for the effect of initial Dt, Dx, and Dv on the final flight time
incertitudes Dt are listed.
There are several situations where not the primary neutral
particles contribute to the initial Dv but, e.g., the ion kinetic
energy released at molecular fragmentation or desorption (such
as in MALDI) or at high space charges due to large ion densities
(relevant for laser-induced ionization). In this case, only large
electric extraction fields help as can be deduced from Equations
(5) and (6). This is in opposite to weak extraction fields needed
for Dx compensation. How to solve this problem is shown in the
following sections. The important role here plays the space
focus of first or second order.
E. Space Focus of First Order
There is a special point in the field-free drift region, where
higher energetic ions (those with positive Dxi: see Fig. 3)
overtake lower energetic ions with DxA ¼ 0 or negative value.
This corresponds to a compression of the primary ion cloud with
an original spread of 2DxA (e.g., in Fig. 3) in the ion source. This
special point, which actually is not a single point but a very
narrow space in the drift region, is called space focus. The
spread of this narrow space depends on the type of ion source as
discussed below. Positioning the ion detector surface at this
space focus results in very small contributions of spatial and
pseudo-spatial incertitude to the ion flight time error Dt. In other
words, the total ion flight time from positions xA þ DxA to
position xSF does only weakly depend on variations of DxA, i.e.,
on the primary spatial distribution. xSF is the distance between
space focus and ion source exit electrode.
In order to find the space focus xSF, we observe the
dependence of total flight time t ¼ f(xA þ DxA) on the ion source
displacement DxA. Flight time t is related to the ion flight path
Mass Spectrometry Reviews DOI 10.1002/mas
 TIME-OF-FLIGHT MASS SPECTROMETRY &

TABLE 1. Different types of flight time incertitude Dt at the ion detector and their origins.

from xA to a point s in the drift region. At s ¼ xSF, the dependence dt 1 tacc 1 tdrift
of t on DxA is minimal. We find the value of xSF by setting the ¼0¼  :
dxA 2 xA 2 xA
first derivation equal to zero: dt/dxA ¼ 0. xSF is called first order
space focus if this is the only fulfilled condition and higher order
derivatives are not considered. For the single stage ion source This delivers the first order space focus of the most basic
one finds: (single stage) ion source. From

Mass Spectrometry Reviews DOI 10.1002/mas 89

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TABLE 2. Countermeasures to reduce flight time errors Dt.

Incertitude Flight time incertitude Countermeasure

in ion source at ion detector

Δt Dtt = Δt Pulsed extraction field EA

Short ionizing laser pulses (< 1 ns)
Fast response time of ion detector

Δx Dtx/t = 1/2 ΔxA/xA Weak extraction field EA

Space focus (see below)

Δv Pseudo spatial error Vertical effusive molecular beama

Dtv-x/t = - 1/2 Ui/U Supersonic molecular beamb
Pseudo temporal error
Dtv-t = mΔvi/qEA Strong extraction field EA c

a
vertical to ion extraction; b
small initial Δv; c problem with Δx–
compensation

rffiffiffiffiffiffi rffiffiffiffiffiffi times tA1 and tA2 and the field-free flight time tSF. The following
3=2 M M equations for the flight times will be developed as function of xA
tacc ¼ 2ðxA Þ C and tdrift ¼ sðxA Þ 1=2
C
EA EA (position of ion formation) since it is the value of xA which
influences the space focus. In addition, the potentials U, UA1,
follows: s ¼ 2xA xSF ð7Þ
and UA2 (with U ¼ UA1 þ UA2) show up in these equations. The
formulas for flight times tA1 and tSF are the same as for tacc and
Unfortunately, the distance s ¼ 2xA in the field-free drift
tSF in the single-stage ion source (see above). The flight time in
region is very short so that clouds of ions with different mass do
the second acceleration region xA2 is described by a flying start
not have sufficient time to separate far enough. Other contribu-
situation: ions enter this region with a kinetic energy qU 
tions (e.g., from ion detection electronics, ion formation time, or
qUA2 ¼ qUA1. All flight time components of a two-stage ion
pseudo-temporal effects) represent a lower limit of Dt at this
source are summarized in Equations (8)–(10). For derivation of
separation time. Therefore, mass resolution R50% ¼ M/DM ¼ 1/2
Equation (9), see Appendix B. Please notice that flight times
t/Dt (with DM ¼ FWHM of mass peak) (see Appendix A) is very
in Equations (8)–(10) are given in two forms: one as a function
small despite a small flight time error Dt.
of the acceleration potentials U, UA1, and UA2 and one as
function of position xA1 in the acceleration region (compare
III. TWO-STAGE ION SOURCE
Eqs. (1) and (2)).
There exist possibilities to increase xSF with respect to xA, rffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffi
namely by a two-stage ion source (Wiley–McLaren approach) M pffiffiffiffiffiffiffi M
tA1 ¼ xA1 2C resp: tA1 ¼ xA1 2C ð8Þ
which consists of two acceleration distances xA1 and xA2 and U A1 EA1
two potentials, the one where the ions are formed and potential
UA2 which is applied to the intermediate electrode (see Fig. 4). pffiffiffiffi pffiffiffiffiffiffiffiffiffi x pffiffiffiffiffi
A2
The total flight time t is now the sum of the acceleration flight tA2 ¼ U  U A1 M 2C
U A2
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffi
M
ffi
resp: tA2 ¼ xA1 EA1 þ U A2  xA1 EA1 2C
EA2
ð9Þ

rffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
M M
tSF ¼ xSF C resp: tSF ¼ xSF C ð10Þ
U xA1 EA1 þ U A2

Two-stage ion sources have new additional features with

respect to single-stage ones. There is now one parameter
FIGURE 3. The first order space focus of a single-stage time-of-flight ion (namely UA2) freely adjustable despite a fixed geometry (xA1,
source. xA2). From the condition dt/dxi ¼ 0 for a first order space focus

90 Mass Spectrometry Reviews DOI 10.1002/mas


FIGURE 4. Top: single-stage ion source with (fixed) first order space focus. Middle: two-stage ion source with
(variable) first order space focus. Bottom: two-stage ion source with (fixed) second order space focus. The space
focus is a position of smallest ion cloud compression as illustrated. A second order space focus reveals a particular
tight ion cloud compression and consequently a high mass resolution.
then follows that xSF is tunable and may be changed to large
values: e.g., xSF ¼ 100 cm for an ion source xA1 þ xA2 ¼ 2 cm.
On the other hand, this free parameter can be used to fulfill a
second condition: d2t/dxi2 ¼ 0 in addition to dt/dxi ¼ 0 and thus
to achieve a so-called second order space focus.
In order to understand the difference between first and
second order space focus concerning better compression ability
for ion clouds, one should consider the following: dt/dxi ¼ 0 is
exactly fulfilled for xi ¼ xA1, only. Figure 1 therefore represents
a simplified view of ion cloud compression. The spread of the
ion cloud at the first order space focus is determined by the
flatness of the function t ¼ f(xA þ DxA) around this extremum. In
many situations, this spread is sufficient, e.g., for a mass
resolution of R50% ¼ 100 for drift lengths of 15 cm. The problem
is that the longer the flight paths xSF of the two-stage ion source
are the worse gets the compression ability of the first order space
focus. This effect limits the mass resolution of linear time-of-
flight mass spectrometers. It can be compensated by considering
higher order derivations of t ¼ f(xA þ DxA) for instance d2t/
dxi2 ¼ 0 in addition to dt/dxi ¼ 0. This means that the function
t ¼ f(xi ¼ xA þ DxA) simultaneously exhibits an extremum and
an inflection point at space focus. This results in a substantially
enhanced flatness of the function (small dependence on xi over a
much larger range of DxA): a second order space focus is then
achieved which exhibits much better compression abilities (e.g.,
R50% ¼ 850 for drift lengths of 13 cm, see Section 5). Similarly
to a single-stage ion source and its first-order space focus
(xSF ¼ 2 xA), also a second-order space focus of a two-stage ion
source is fully determined and solely dependent on the ion
source geometry. Further details, such as the relation between
xSF-2.order, xA1, and xA2, will be discussed in Section 5. The
situation for two-stage with respect to single-stage ion sources is
illustrated in Figure 4.
Despite this nice feature, the problem between Dx and Dv-
compensation (a weak electric extraction field is needed in the
former, a strong one in the latter case) is not solved yet. In
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
particular, large initial velocity distribution and space charge
effects bring linear time-of-flight mass spectrometers soon to the
limits of their possibilities. For instance, in the so-called Wiley–
McLaren approach xSF is increased strongly. This considerably
worsens the ion cloud focusing features in the space focus which
still is of first-order. On the other side, the consequence of
choosing a second order space focus is a weak electric field EA1.
This increases the influence of initial velocity distributions and
thus the pseudo-spatial and pseudo-temporal error considerably.
The so-called time-lag-focusing introduced by Wiley and
McLaren was a first trial to cope with this problem. By delayed
extraction after ion formation initial velocities were transformed
into initial spatial distribution (a kind of pseudo-spatial error).
Unfortunately, this destroys the general feature that all measures
to compensate for flight time errors based on electric fields are
mass independent. Corrections achieved by time-lag-focusing
therefore are only valid in certain mass ranges.
Here the so-called reflectron-time-of-flight mass spectrom-
eters come into play. In this ToF-MS type, ion source and ion
reflector may share the tasks of compensating the effects of
original temporal, spatial, and velocity distributions. Thus, the
one may be responsible for spatial and pseudo-spatial error
compensation, the other for compensation of pseudo-temporal
effects.
IV. REFLECTRON-TIME-OF-FLIGHT MASS
SPECTROMETER
Since its invention by Mamyrin (Mamyrin et al., 1973),
reflectrons of many different types have been developed from
multiple-reflection instruments with very high mass resolution
(Hanson, 2000; Casares, Kholomeev, & Wollnik, 2001, Plaß
et al., 2007), to broad energy accepting instruments (Vlasak
et al., 1996), miniaturized cylindrical ion mirrors (Vialle et al.,
1997; Zhang & Enke, 2000), or so-called end-cap reflectrons
(Cornish & Cotter, 1997; Fancher, Woods, & Cotter, 2000). In
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the following, the most common reflectron with one ion mirror
is discussed as introduced by Mamyrin and coworkers.
The common reflectron ToF-MS consists of an ion source
(single- or double-spaced acceleration region), a field-free drift
region and an ion reflector. Ions are accelerated in the ion source,
path the field-free drift region, are reflected in the ion reflector,
again path part of the field-free drift region and hit the ion
detector surface. The field-free region may be subdivided into a
field-free distance xSF between the end of the last electrode of
the ion source and its space focus, a field-free distance xD1
between this ion source space focus and the front electrode of
the ion reflector, and finally a field-free distance xD2 between
this reflector front electrode and the surface of the ion detector.
This concept is displayed schematically in Figure 5. There, ion
source as well as ion reflector are equipped with two stages.
In the ion source, these represent the acceleration distances xA1
and xA2 within the electric fields EA1 and EA2. Correspondingly,
the total kinetic energy of the ions entering the field-free drift
region is qEA1 xA1 þ qEA2 xA2 ¼ qEA1 xA1 þ qUA2 ¼ qU. UA2 is
the potential at the intermediate ion source electrode. The
electric field EA1 is (UHV  UA2)/LIONS. UHV is the potential at
the first electrode (pushing electrode) of the ion source, LIONS
is the distance between pushing and intermediate electrode.
The electric fields EA1 and EA2 are assumed to be homogenous.
We will now deal the ion source and the field-free drift region up
to the space focus SF of the ion source as a first time-of-flight
unit.
Similarly to the ion source, the ion reflector consists of two
stages, a deceleration or re-acceleration region xS, respectively,
and a reflecting region xR with the electric fields ES ¼ US/xS and
ER ¼ (UREF  US)/LREF. UREF is the potential at the ion reflector
end plate, LREF is the length of the second stage (ion reflecting
field). xR is the penetration depth of the ions into the reflecting
field and depends on the kinetic energy the ions achieved in the
ion source due to qER xR þ qUS ¼ qU. Again it is assumed that
the electric fields ES and ER are homogenous. In some modern
reflectron developments, this is not the case anymore but this
will not be treated here (Doroshenko & Cotter, 1999; Gardner &
FIGURE 5. Scheme of a reflectron-ToF-mass analyzer. SF: Ion source space focus point.
92
Holland, 1999; Zhang, Gardner, & Enke, 2000). Following the
example of the ion source, we will deal the field-free drift
regions xD1 and xD2 and the ion reflector as second time-of-flight
unit. For illustration of the functional principle of reflectrons, we
assume that both field-free drift regions xD1 and xD2 are equally
long. A generalization will follow later. For reasons of symme-
try, the flight times from the ion source space focus to the turning
point in the ion reflector and the flight time from this turning
point to the surface of the ion detector are then equal.
One may now treat the ion reflector and its second drift
region xD2 as an ion source with field-free drift region (ion
exiting phase) and the ion flight region xD1 together with the way
within the ion reflector down to the point of ion return as its
mirror image (ion entering phase). It is evident that then for both
phases the same formulas are valid with the only difference that
the time is reversed making out of acceleration a deceleration. It
is also obvious that these formulas are the same as for a two-
stage ion source as given in Section 3. Correspondingly, one
may find a space focus of the ion reflector in its ion exiting mode
and in its ion entering mode by choosing the right size of xD1,
xD2, xS, and xR.
It obviously is very reasonable to position the space focus
of the exiting mode on the detector surface and the one of the
entering mode at the ion source space focus SF. In this case, all
ions starting at the same time but at different positions within the
reflecting field (exiting mode) will arrive at the same time at the
detector surface. This corresponds to optimal compensation of
the spatial distribution of the ions within the ion reflecting field.
Due to symmetry reasons, this is also true for the entering mode
but with time reversal. In other words, all ions of one distinct
mass starting exactly at the ion source space focus point SF at
the same time but with different kinetic energies will stand still
in the ion reflecting field at the same time but at different
positions. These are determined by their different ion kinetic
energies which are transformed into the corresponding potential
energies. All other ions of the same mass which pass the ion
source space focus point SF at different times DtSF will reach
their turning point in the ion reflecting field and therefore the ion
Mass Spectrometry Reviews DOI 10.1002/mas

detector surface at time differences DtSF. That means DtSF
behaves like a true time error (see Eq. (3)) with respect to the
compensation of distributions of time, space, and velocity in the
ion reflector.
This situation may also be expressed in the following way:
the ion clouds at the ion source space focus are imaged onto
the ion detector surface by the space-focus-compensating ion
reflector. In the ideal case (optimal compensation in the ion
reflector), the temporal incertitude DtSF with which the ions of
one mass pass the ion source space focus point SF is equal to the
temporal incertitude of arrival at the ion detector. On the other
hand, the total ion flight time is considerably enlarged with
respect to the flight time from ion formation to ion source space
focus SF. Due to a constant Dt, the resolution R50% ¼ 1/2 t/Dt
then increases, respectively.
The question arises if ideal compensation of ion kinetic
energy distributions (corresponding to spatial or pseudo-spatial
errors) is possible for an ion reflector. Do not exist the original
problems also here, such as that of large distances to first order
space foci (the quality of ion cloud compression is reduced) or
that of space foci of second order (weak electric fields result in
large pseudo-temporal errors called “turn-around-time”)? Con-
cerning this question, an intrinsic difference of ion source and
ion reflector comes into play: in the ion reflector, all ions are
reflected, i.e., there is a moment where they are standing still. In
the symmetric case (xD1 ¼ xD2), all ions of the same mass but of
different kinetic energy even do this at the same time. That
means there is an instant of time where all ion velocities in
direction of ion extraction (i.e., ion reflection) are equal to zero.
If we treat the exiting mode of the reflector as a kind of pseudo-
ion source then there does not exist an initial velocity distribu-
tion and therefore no “turn-around-time.” Also space charge
effects do not play a role since the ions have a large distance
from each other due to the mass-dependent stretching in time
and the large distribution in space. Kinetic energy released from
fast dissociation processes is also not a problem since these
processes are fast and therefore only take place in the ion source.
In conclusion, a weak electric field ER is not problematic
anymore. This is an ideal situation for working with a second
order space focus and for achieving good ion cloud compression
even for large distances xD1 and xD2.
The total time-of-flight error Dt at the ion detector therefore
is composed as following:
Dt ¼ Dt1 ðturnaroundÞ þ Dt2 ðion sourceÞ þ Dt3 ðion reflectorÞ
þDt4 ðfixÞ ð11Þ
Dt1 is due to the pseudo-temporal error of the ion source
and can be kept small by a high electric field EA1 for ion
extraction. This is now acceptable since the distance xSF
from ion source to space focus has not to be large (this would
only be possible with weak extraction fields). The task of
mass separation by long flight times is now taken over by the
ion reflector and the field-free drift regions xD1 and xD2 (see
Section 4).
Dt2 is the residual spatial and pseudo-spatial error of the ion
source. Due to small xSF and therefore flight times tSF to the ion
source space focus SF, Dt2 may be neglected in comparison to
Dt3 which is the residual non-corrected part of the spatial error
of the ion reflector.
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
Dt3 is due to the finite compensation of the spatial error in
the ion reflector. It cannot be neglected despite second order
space focusing because of the large distances xD1 and xD2 from
ion source space focus SF to the reflector front electrode and
from there to the ion detector, respectively.
Dt4 is the sum of all fixed temporal errors such as the ion
formation time (e.g., ionizing laser pulse length) and the ion
detector response time.
Finally, some considerations about the two field-free drift
regions xD1 and xD2 have to be made. Up to now, for symmetry
reasons xD1 ¼ xD2 has been assumed. However, the compensa-
tion effect depends only on the ratio of the time the ions spend in
the field-free drift region to that they need to pass the ion
reflector. The partitioning of the time the ions spend in the field-
free drift region between distances xD1 and xD2 therefore does
not play a role as long as the sum of both stays constant:
xD1 þ xD2 ¼ xD. So, xD1 and xD2 may have different size, only the
total path length in the field-free drift region xD counts.
V. SPACE FOCUS OF TWO-STAGE ION SOURCES
AND ION REFLECTORS
In this section, formulas for the first and second order space foci
of two-stage ion sources and ion reflectors are deduced. For
comparison see Mamyrin et al. (1973), furthermore, consider
Schlag (1994), Guilhaus (1995), Grotemeyer (2001), Wollnik
(2013), Radionova, Filippov, & Derrick (2015) and references,
cited herein. In the following, unified parameters are introduced
which can be applied to both systems and allow a simplified way
of deduction of such formulas.
Geometrical magnitudes (first and second acceleration
region, field-free drift region)
a for xA1 or xR b for xA2 or xS c for xSF or 1/2 xD
Electrical magnitudes (electric fields)
A for EA1 or ER B for EA2 or ES
The total flight time t ¼ ta þ tb þ tc results from Section 2.
Obviously, the expression (2C M1/2) may be factored out and a
reduced flight time t ¼ t (2C M1/2)1 may be introduced for
further simplification. t does not depend on the ionic mass
anymore. Therefore, the following formulas for the compensa-
tion of flight time errors in the space focus are valid for the
whole mass range from 1 to infinity.
1 1 1 c
t¼ ðaAÞ1=2 þ ðaA þ bBÞ1=2  ðaAÞ1=2 þ ðaA þ bBÞ1=2
A B B 2
ð12Þ
The effect of a spatial error Da on the reduced total flight
time t may be represented by the Taylor series f(x) ¼ f(x0) þ f0
(x0) Dx þ 1/2 f00 (x0) Dx2 þ . . ..1/n! fn(x0) Dxn. The first, second,
and third derivations f0 (x0), f00 (x0), and f000 (x0) of t with respect of
a are as follows:

dt 1
¼þ A
1 1 1
ðaAÞ1=2 þ ðaA þ bBÞ1=2  ðaAÞ1=2
da 2 A B B

c 3=2
 ðaA þ bBÞ ð13aÞ
2
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 Using Ub ¼ U  Ua and R ¼U/Ua one obtains Equation (17):

d2 t 1 2 1 1 1
¼  A ðaAÞ3=2 þ ðaA þ bBÞ3=2  ðaAÞ3=2  
da2 4 A B B 1
 c ¼ 2R3=2 a  b pffiffiffi ð17Þ
3c
 ðaA þ bBÞ5=2 ð13bÞ Rþ R
2
The following conclusion for a linear time-of-flight mass
spectrometer can be drawn from Equation (17). For a long drift

d3 t 3 3 1 1 1 region c ¼ xSF between ion source and space focus (needed for
3
¼ þ A ðaAÞ5=2 þ ðaA þ bBÞ5=2  ðaAÞ5=2 good mass resolution) potential Ua has to be small and distance
da 8 A B B
 a has to be large, respectively. This corresponds to a weak
5c extraction field in the first acceleration region. In Section 2, it
 ðaA þ bBÞ7=2 ð13cÞ
2 has been discussed that this is unfavorable for compensation of
flight time errors which are caused by distributions of initial
velocities. A second conclusion is that the first order space focus
In an ideal space focus, the ionic flight time would be totally
may be shifted by variation of R ¼ U/Ua despite fixed ion source
independent on the spatial error Da. Hereby, Da includes the
geometry given by fixed distances a and b. A third conclusion is
spatial distribution of ions around the point of ion formation as
that all space focus conditions are still fulfilled if all voltages are
well as the pseudo-spatial distribution due to distribution of
changed by the same factor (i.e., R is constant). Thus, high
initial velocities. In reality, a first order space focus is achieved
electric fields may be chosen for small “turn-around-times”
if the first term of the Taylor series disappears due to dt/dt ¼ 0.
without changing the space focus conditions. This is also true
A second order space focus is existent if the second term
for second order space foci, which are discussed in Section 5.2.
disappears as well: dt/da ¼ 0 and d2t/da2 ¼ 0.
Equation (17) may be tested by the two limiting cases:
1: order :
1. Single-stage ion source: b ¼ 0 and Ua ¼ U (corresponding
    to R ¼ 1): ! c ¼ 2a (This accords with Eq. (7)).
1 1 1 c
0¼  ðaAÞ1=2 þ  ðaA þ bBÞ1 ðaA þ bBÞ1=2 2. Quasi-single stage ion source: b ¼ a and Ua ¼ Ub ¼ 1/2 U
A B B 2 (corresponding to R ¼ 2): this corresponds to a single-stage
ð14aÞ ion source with acceleration region 2a.
  pffiffiffi
1 pffiffiffi 2 þ 2  1
c¼22 3=2
aa pffiffiffi ¼ 4a 2 pffiffiffi
2: order : 2þ 2 2þ 2
pffiffiffi
    pffiffiffi 2þ1
0¼
1 1
 ðaAÞ 3=2
þ
1 3c
 ðaA þ bBÞ1
ðaA þ bBÞ3=2 ¼ 4a 2 pffiffiffi pffiffiffi
! c ¼ 4a
A B B 2 2 2þ1
ð14bÞ
(This accords with Eq. (7), too).
Equations (14a) and (14b) may be reformulated using the
potentials Ua, Ub, and U with Ua ¼ aA, Ub ¼ bB, and U ¼ Ua þ
Ub ¼ aA þ bB (remember: qU is the total ion kinetic energy
with q ¼ ion charge). B. Second Order Space Focus
    Both Equations (15) and (16) have to be fulfilled if a second
a b 1=2 b c1
1: order : 0 ¼  Ua þ  U 1=2 ð15Þ order space focus is intended. Thus, a second equation
Ua Ub Ub 2 U determines the relation of geometric magnitudes and electric
potential ratio R. Consequently, distance c and ratio R are fully
    determined if the distances of the two-stage electrode arrange-
a b b 3c 1 ment is fixed (fixed distances a and b). A second order space
2: order : 0 ¼  U a 3=2 þ  U 3=2 ð16Þ
Ua Ub Ub 2 U focus of a given two-stage ion source therefore cannot be shifted
anymore by variation of R as in the case of a first-order space
focus. To calculate this relation, it is feasible to multiply
Equation (15) by Ua1 and then set it equal to Equation (16).
A. First Order Space Focus
The terms containing Ua3/2 cancel each other. Multiplying by
Equation (15) (first order term ¼ 0) can be solved for c which is U2 and using U/Ua ¼ R and U/Ub ¼ R/(R  1) (see Appendix C)
the field-free drift region to the first order space focus. gives Equation (18):
   
a b b 3=2c 3c
c ¼ 2U 3=2 U a 1=2  þ U 1=2 R¼ ¼ ð18Þ
Ua Ub Ub c=2  b c  2b
  
3=2 Ua 1=2 In practical use the potential Ub (voltage at the intermediate
¼ 2ðU=U a Þ ab 1  ðU=U a Þ
Ub electrode of an ion source or decelerating voltage at the second

94 Mass Spectrometry Reviews DOI 10.1002/mas


grid of an ion reflector) plays a major role. Therefore Equation
(18) is reformulated:
U b R  1 3c  c þ 2b 2c þ 2b
¼ ¼ ; Ub ¼ U ð19Þ
U R 3c 3c
Ion reflectors are mostly designed with short deceleration
fields: xS << 1/2 xD (see Fig. 5) or b << c, respectively. Under
these conditions, an approximation for R (Eq. (18)) is R  3 and
for Ub (Eq. (19)) is
U b ¼ 2=3U for b
c ð20Þ using two- or multi-photon absorption (Boesl, Neusser, &
Using R  3 in Equation (17), delivers an approximation for
c at the condition of small b-values:
c  10:5a for b
c ð21Þ direction of ion extraction) using a micrometer screw. The
For b ¼ 1/6 a one obtains c ¼ 10.5 a corresponding to
b ¼ 0.016 c, for b ¼ 0 one obtains c ¼ 10.4 a. Inserting Equation
(18) into Equation (15) results in a general geometrical relation
of a, b, and c for a second order space focus (for details see
Appendix D):
  !
c  2b c  2b 3=2
a¼ bþc ð22Þ
2c þ 2b 3c
The geometric and electric details of ion sources or ion
reflectors with second order space focus have now been
determined. The next step is to determine total ion flight time
and residual errors Dt ¼ f(DU). Hereby, the short flight time tIS
from the point of ion formation to the ion source space focus SF
is assumed to be <5% of the total flight time corresponding to
xSF  0.05 xD (see Fig. 5 for xSF and xD).

The approximation for tIS is then:
tIS  0.05 xD (M/U)1/2 C (IS for ion source).

The flight time in the field-free drift region c ¼ 1/2 xD is
tc ¼ c (M/U)1/2 C.

The flight time in the deceleration region b ¼ xS of the ion
reflector is approximately
tb > b (M/U)1/2C ¼ 0.02 c (M/U)1/2 C (assuming b  0.02 c).

The flight time in the reflecting field over a distance of
a ¼ xR from entering till stopping is
ta ¼ a (M/Ua)1/2 2C  0.33 c (M/U)1/2 C (see Appendix E).
The flight time from ion formation to ion detector in a
reflectron TOF-MS with short deceleration field is then t ¼ tIS þ
2tc þ 2tb þ 2ta  {0.05 þ 2 (1 þ 0.02 þ 0.33)}c (M/U)1/2 C or
rffiffiffiffiffi rffiffiffiffiffi
M M
t  2:7c C þ tIS  1:4xD C ð23Þ
U U
The total flight time error consists of (i) the residual ion
reflector error Dt/t ffi kR (DU/U)3 corresponding to non-vanish-
ing third and higher order terms (see Eq. (13c)), (ii) the residual
ion source error Dt/tQ ffi kQ (DU/U)3 if the ion source is also run
in second order correction, (iii) the turn-around time error
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
Dt ¼ 2 C (M Ui)1/2/EA1 determined by the conditions in the ion
source, and (iv) fixed time errors DtFIX, e.g., due to the ion
detector response time. In the following, we consider contribu-
tions (i) and (ii) which correspond to compensation of real or
pseudo-spatial ion distributions resulting in space foci. The best
way to determine the quality of compensation of an individual
reflectron is the graphical representation of Dt ¼ f(DU) or Dt/
t ¼ f(DU/U), respectively. The measurement of such depend-
ences is possible by determining total ion flight times while
varying the position xA1 of ion formation.
Such a variation is easily achieved with laser ionization
Schlag, 1978; Boesl, 1999). Hereby, the laser is focused at a
position in the field EA1 of the ion source where the ions are
produced. The focusing lens is shifted perpendicularly to the
laser beam and parallel to the axis of the ion source (i.e.,
reading of this screw then will directly give the amount of DxA1,
which is the shift of the position of ion formation, with an
accuracy of 0.01 mm. This is because parallel light (such as a
laser beam) always is focused onto the axis of the focusing lens.
The shift of a lens (i.e., of its axis) therefore is equal to the shift
of the laser focus. Since DU ¼ DxA1 EA1, dependencies Dt ¼
f(DU) can be scanned by shifting the laser focus step by step.
Figure 6 displays theoretical and experimental curves for
relative flight time changes Dt/t as function of relative spatial
shifts DxA1/xA1 which is equivalent to relative energy changes
DU/U. One should be aware that for this method, small enough
laser intensities have be used to avoid high ion densities and thus
space charge effects which will cause “initial velocity distribu-
tion” and thus additional flight time broadening (see later
discussion).
The graphs in Figure 6 are calculated or measured at a
reflectron of a drift length xD ¼ 160 cm and an ion energy of
600 eV. The theoretical curve 1 displays the cubic part of Dt/t ¼
f(DU/U) (see Eq. (13c)) if the ion reflector is compensated in
second order. Within a small relative energy range DU/U ¼
 2.5%, curve 1 shows a change of Dt/t of less than 0.5 105.
This would correspond to a mass resolution R50% ¼ M/DM ¼ 1/2
t/Dt ¼ 100,000 (in praxis other flight time errors would dominate
here). However, for larger energy changes the mass resolution
would decrease strongly, e.g., for DU/U ¼  8.5%, R would be
R ¼ 1/2 (24 105) ¼ 2,000. This small range of compensation
can be improved significantly by the following trick. The
voltages of the ion reflector are changed in such a way, that not
first and second order term vanish, but that the sum of second
and third order term get minimal. Graph 2 in Figure 6 displays
the corresponding curve Dt/t ¼ f(DU/U). One can realize that in
the range DU/U ¼  2.5%, the maximal mass resolution is not
achieved anymore but in the enlarged energy range DU/U ¼
 8.5% the mass resolution is now as large as R50% ¼ 8,500.
The measured curve 3 reveals an even larger energy range
of acceptance of DU/U ¼  9.5% for the same mass resolution.
The asymmetry of curve 3 is due to higher order terms of the ion
reflector and quadratic terms of the ion source space focus. In
Figure 6 as in the whole Section 5 dealing with space focus
conditions, only flight time errors due to initial spatial or
pseudo-spatial distribution (caused by initial velocity distribu-
tion) in the ion source are accounted for. Temporal (e.g., 10 ns
ion formation time due to laser pulse length) or pseudo-temporal
errors (e.g., turn-around-time) are not respected. In addition,
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FIGURE 6. Calculated and measured curves Dt/t ¼ f(DU/U). (1) Theoretical curve with dt/dxA1 ¼ 0 and d2t/
dxA12 ¼ 0 (general formulation by Eqs. (13)–(16)). Higher order terms are neglected. (2) Theoretical curve with
dt/dxA1 ¼ 0 and d2t/dxA12 þ d3t/dxA13 is minimal. Second and third order terms cancel each other as far as
possible, higher order terms are neglected. (3) Measured curve of reflectron compensated for large DU/U.

there exist other sources of flight time error for an ion reflector
which also are not included here and are discussed in Section 6.
A special form of initial velocity distribution is caused by space
charge. Its effect on the mass resolution also is subject of Section
6. Typically, a mass resolution between R50% ¼ 1,500 and 3,000
for mass 100 should routinely be achievable in a reflectron with
xD ¼ 160 cm and ion kinetic energies of 600 eV. An example is
displayed in Figure 7 for the parent ion of benzene, its (MH)þ
and (MH2)þ fragment ions as well as its 13C1-isotopomer.
With the same instrument as in Figure 7, a mass spectrum
of angiotensin, a peptide with 10 aminoacids and the molecular
mass of 1,295 m/z, has been measured and a resolution of
R50% ¼ 6,000 has even been achieved. The reason for this
increased mass resolution is that for small masses fixed time
errors DtFix are an important contribution to the total flight time
error. For large masses, these fixed errors play less and less role
since t as well as Dt (e.g., caused by spatial distributions or space
focus) scale with the square root of the ion mass. Therefore in an
intermediate mass range, the mass resolution of ToF-MS
instruments increases with increasing mass. The power of
second order compensation even for simple, linear ToF-mass
spectrometers is demonstrated in Figure 8.
If one takes care that initial velocity distribution, e.g., due
to space charge effects, as well as fixed time error do not play a
role (i.e., Dtv << Dtx and Dtt << Dtx, see Eqs. (3)–(6)) then
even in short linear flight time mass spectrometers a respectable
mass resolution is achievable. In Figure 8, the field-free drift
region xSF was as short as 13 cm. Nevertheless, a mass resolution
of R50% ¼ M DtDM ¼ 1/Dt ¼ 106 52/6.5 ¼ 850 for xylene with a
molecular mass of 106 m/z was possible (the used formula for
R50% is explained in Appendix A).
VI. FURTHER SOURCES OF FLIGHT-TIME ERRORS
The mass resolution discussed in Section 5 is an upper limit and
only caused by spatial distributions of ions in the ion reflector
and the ion source (see Eq. (4)). Other sources of flight time
error have already been discussed such as fixed time incertitude
(see Eq. (3)) and initial velocity distribution in the ion source
(see Eqs. (5) and (6)). A special case of the latter is the space
charge effect which may play a role at ionization in the focus of
laser beams and is discussed in Section 6.3. Two other sources
of flight time error have to be considered if one aspires to
particularly high mass resolution. On the one hand, divergence
and width of the ion beam may cause a broadening of flight time

FIGURE 7. Time-of-flight mass spectrum of benzene radical cation,

fragment ions due to H and H2-loss and the 13C1 12C5 H6-isotopomer in its FIGURE 8. Scheme of a short linear ToF-mass spectrometer and the mass
natural isotopic mixture measured with a home-built reflectron. A typical spectrum displaying the molecular ion of xylene and its 13C-isotopomer.
mass resolution of R50% ¼ 1,500 is achieved. Mass resolution of R50% ¼ 850 is achieved.

96 Mass Spectrometry Reviews DOI 10.1002/mas


peaks. On the other hand, scattering of ions at the metal grids,
which are commonly used to achieve linear electric fields in the
ion reflector, can limit mass resolution.
A. Scattering of Ions at the Grids of Ion Reflectors
One effect of grids is reduced transmission due to collision of
ions with the wires of the grid. Optimal grids have an optical
transmission of 90–95%. On the other hand, ions passing near
such wires may be deviated from the optimal ion trajectories by
small inhomogeneous electric fields. This effect may be large
enough to induce a further reduction of transmission or small
enough so that the ions still hit the ion detector but do this at
different positions than the non-disturbed trajectories. This
results in ion flight time changes causing a broadening of ion
flight time peaks. In the following, a short estimation of
scattering angles is performed. As maximum angle by which
ions are deflected at an opening between an electric field and a
field-free region (field distortion at a single mesh of the metal
grid) it can be assumed (Verster, 1963):
tan g max
1=8 D E 1=U Ion ð24Þ
where D is the diameter of the opening (i.e., width of a single
mesh, typical example D ¼ 0.035 cm), E electric field on the one
side of the grid (i.e., the decelerating field ES ¼ US/xS, typical
example ES ¼ 200 V/cm), and eUIon ion kinetic energy (typical
examples: at the first grid UIon ¼ 600 V, at the second grid
UIon ¼ 200 V, since ions lose 2/3 of their energy in the
decelerating field (see Eq. (20)).
Equation (24) is valid for the condition D E << UIon. For
each mesh of the grid this is easily fulfilled. As can be seen from
Figure 9, there are four spots in the ion reflector where ions are
scattered. Due to the much smaller ion kinetic energies at the
second grid, the scattering at this grid is significantly larger.
Therefore we deal the scattering at grid 2 as the dominating
effect. From Equation (24) and the numbers just given one
obtains as a maximum angle:
tang max ¼ 4:4 103 ; g max ¼ 0:25
FIGURE 9. Scattering of ions at grid 2 and its effect on ion flight path for
detector orientation A and B.
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
Let us consider the scattering of the reflected ion beam in
more detail (see Fig. 9). The flight time error caused by the
scattering strongly depends on the orientation of the ion detector
surface. In orientation A (see Fig. 9), it is perpendicular to the
main ion trajectory, in orientation B it is parallel to the grid of
the ion reflector. The following estimations are performed for
M ¼ 106 (xylene), U ¼ 600 eV, angle a0 ¼ 4˚ between central
ion trajectory and normal of ion reflector grid surface, and
xD2 ¼ 60 cm.
Orientation A: a scattering angle of 0.25˚ causes a flight
time change of about 1 nsec. The divergence of the ion beam
will cause a much larger flight time broadening (see Section
6.2).
Orientation B: this divergence effect (see Section 6.2) can
be reduced by turning the detector into position B, however, at
the expense of an increased scattering effect. The vertical (to ion
trajectory) deviation on the detector surface (see Fig. 9) is
Dy ¼ xD2 tan gmax ¼ þ 0.26 cm and causes a flight path change
of DxD ¼ Dy tan a ¼ 0.26 tan 4˚ ¼  0.018 cm and thus a change
of ion flight time DtD ¼ DxD (M/U)1/2 0.72 [msec] ¼  5.4 nsec.
B. Influence of the Ion Beam Divergence
Commonly, the ion beam enters the ion reflector at an angle a0
between central ion trajectory and normal of ion reflector grid
surface. This allows placing ion source and ion detector side by
side. However, the ion reflector only acts on ion velocity
components perpendicular to the equipotential surfaces of the
electric field. Therefore, the magnitudes U and DU (with the ion
kinetic energies eU) which are relevant for the space focus
conditions of the ion reflector have to be replaced by U cos2a0
and DU cos2a0. In a typical reflectron, a0 ¼ 4˚ and cos2
a0 ¼ 0.995. This results in minimal changes of space focus
conditions. Flight time broadening comes into play if a variation
of angle a0 by Da occurs due to the divergence of the ion beam.
In our example (M ¼ 106, eU ¼ 600 eV, xD ¼ 160 cm, Ndetector ¼
2 cm), the divergence determined by detector surface size and
trajectory length is Da ¼ 0.012 rad (see Appendix F).
There are two contributions to flight time broadening Dt,
one arising in the field-free drift regions xD1 and xD2 and one in
the reflecting field Eref of the ion reflector. The latter is due to the
fact mentioned above that only the velocity component parallel
to the axis of the ion reflector is affected by the decelerating and
reflecting fields. This results in a reduced ion kinetic energy. The
consequence is that the ions do not penetrate so far into the
reflecting field and therefore the dwelling time in this field is
reduced. An estimation of Dt for M ¼ 106, eU ¼ 600 eV,
xD ¼ 160 cm, and a divergence of Da ¼ 0.012 rad gives Dt ¼  5
nsec for trajectory b and a, respectively (see Fig. 10 and
Appendix F).
The second contribution to Dt is due to different lengths of
trajectories in the field-free region. This difference of Dx ¼ Dxout
 Dxin gives rise to a flight time difference of Dt ¼  10 nsec for
trajectory b and a, respectively (see Fig. 10 and Appendix F).
Both effects are negative for trajectory a and positive for
trajectory b. In total, both flight times add up to a difference of as
much as 34 nsec. This flight time error can be reduced by
rotating the detector around an axis perpendicular to the ion
reflector axis and the ion trajectories so that the detector surface
gets more parallel to the ion reflector grids. This shortens
trajectory b and elongates trajectory a. Therefore it is very useful
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FIGURE 10. The influence of incidence angle a0 and ion beam divergence
on flight time broadening.
to consider a detector mount rotatable with a micrometer screw
when planning a home-built reflectron with good mass
resolution.
C. Space Charge Effects
Let us consider an ion cloud with spherical symmetry. Its size
may be determined by the overlap of molecular beam and laser
focus which are perpendicular to each other as in Figure 11. As
an example, we assume a radius of the ion cloud of r0 ¼ 50 mm
due to a laser focus diameter of 100 mm. In this ion cloud, a total
ion number of N ¼ 5 104 ions of mass M ¼ 106 u is assumed (for
typical numbers at multiphoton ionization see Appendix G).
Large accelerating electric fields will exist in such an ion cloud;
they will change in time during expansion of the cloud and a
distribution of momentum into all directions will occur. It is
obvious that such a scenario will result in significant flight time
broadening. To gain a first insight to the problem, an estimation
of the average energy qUi of a single ion in an ion cloud due to
space charge is given in Equation (25). It is assumed that the
electron cloud separates from the ion cloud after ionization in
less than 1 nsec due to secondary electron excess energy and that
the ion cloud is spherical and homogeneously charged (for
derivation of Eq. (25), see Appendix H):
3  N  e2
qU i ¼ ð25Þ
5  4p  e0  r0
For the above numbers for N and r0, one obtains an average
energy per ion of qUi ¼ 0.8 eV. We assume that after short time
FIGURE 11. Ionization volume in the case of focused (a) and unfocused
(b) laser beam.
98
most of this potential energy has been converted into kinetic
energy and thus the ions gain extra initial velocities. The pure
ion kinetic energy contribution to flight time incertitude will
easily be compensated in the space focus of the ion source. The
problem is the pseudo-temporal contribution (see Section 2.3).
To get an impression of its magnitude, we use Equation (6):
pffiffiffiffiffiffiffiffiffiffiffiffiffi
Dtpseudo ðspace chargeÞ½s ¼ 144  104 U i  M =EA ð26Þ
For Ui ¼ 0.8 V, M ¼ 106 au, and the acceleration field
EA ¼ 105 V/m, one obtains Dt ¼  13 nsec. For a total flight time
of 60 ms, this reduces mass resolution to R50% ¼ 1/2 t/Dt ¼ 1/2
60/0.026 ¼ 1,150. Countermeasures are increase of electric field
EA and, in particular, decrease of Ui. The latter can be reached
by using larger laser foci or even an unfocussed laser beam.
Since two-photon ionization (the most common type of multi-
photon ionization) depends quadratically on the laser light
intensity defocusing will strongly decrease ionization efficiency
(see Appendix G). For instance, a change from r0 ¼ 50 mm to
r0 ¼ 500 mm increases the laser beam cross section by a factor
of 100, and consequently decreases the laser beam intensity by a
factor of 102 and the ionization efficiency IE by a factor of
104. On the other hand, the illuminated volume will increase
by (r0 /r0)2  l/2r0 ¼ 100  10 due to the 100 times larger cross
section and the 20 times longer ionization volume if l ¼ 2 mm is
assumed (l is the width of the molecular beam as illustrated in
Fig. 11). The number of ions in the ionization volume for the
unfocussed laser beam (r0 ¼ 0.5 mm, l ¼ 1 mm) then is:
N unfocussed ¼ N focussed  V unfocussed =V focussed  IEunfocussed =
IEfocussed ¼ 5 104  103  104 ¼ 5 103
With the numbers N ¼ 5 103 and r0 ¼ 0.5 mm, Equation
(25) gives an initial energy of qUi ¼ 0.008 eV. From this, a
Dtpseudo(space charge) ¼  1.3 nsec results which is a very
reasonable value and is in the range of other fixed time errors as
the ion detector response time. Although the consideration given
above includes large simplifications and even may underesti-
mate the influence of space charge, it gives insight into this
effect and its dependence on relevant parameters and allows the
user to optimize time-of-flight mass analyzers for own purposes.
D. Further Measures to Increase Mass Resolution
1. Gridless Ion Reflectors
Scattering of ions at the grids of ion reflectors can be avoided by
using gridless ion reflectors. Of course, the electric fields there
are not homogeneous due to large extensions of the electric field
into the former field-free drift region. Analytical formulas as
given above do not hold anymore and may only serve for
qualitative consideration. Numerical calculations (e.g., using the
SIMION software (see www.simion.com)) have to be used to
determine space focus conditions. The curved electric fields at
the transition from drift region to ion reflector may have an
additional advantage: they may act as a large ion lens and thus
increase the overall ion transmission.
In Figure 12, part of the mass spectrum of para-xylene is
displayed showing the molecular ion mass peak and its 1C13-
isotopomere in its natural abundance. In addition to a gridless
Mass Spectrometry Reviews DOI 10.1002/mas

FIGURE 12. Mass peak of p-xylene and its 1C13-isotopomer measured
with a reflectron with gridless ion reflector: xD ¼ 160 cm, Uion ¼ 700 eV,
laser beam diameter 1 mm, laser pulse length 1.5 nsec. The mass spectrum
reveals a mass resolution of R50% ¼ 10,270 (Walter, Boesl, & Schlag, 1986).
ion reflector and a drift region of xD ¼ 160 cm (xD1 ¼ xD2 ¼
80 cm) measures were taken to keep the fixed temporal
contribution Dtt and the pseudo temporal contribution Dtvt to
the flight time incertitude as small as possible. Using laser
ionization, the typical laser pulse length of 10 nsec represents a
serious incertitude. It has been reduced by “cutting” the laser
pulse using a passive saturable absorber. A pulse length of
1.5 nsec has been achieved at the expense of laser pulse energy,
however. The most important pseudo temporal contribution
at laser ionization is due to space charge. This has been
reduced by using an unfocussed laser beam with a cross section
of 1 mm2. The influence of initial thermal velocities of the
neutral precursor molecules has been reduced by vertical
arrangement of ion extraction and molecular beam. The latter
had a small angle of spread giving rise to a small velocity
component in direction of ion extraction. A mass resolution of
R50% ¼ M DtDM ¼ 1/Dt ¼ 10,270 has been achieved by these
measures.
The somewhat unfavorable method (smaller total ion
numbers) to reduce temporal contribution by cutting the laser
pulse and defocusing the laser beam can be compensated by
alternative means such as pulsed extraction fields in the ion
source and the use of high-rep-rate pico- or even femtosecond
lasers.
3. Pulsed High Voltage Ion Source
Laser pulse cutting can be replaced by a pulsed ion source. This
is realized by applying a high voltage pulse to the ion source
electrodes after the ionization process. Ions are formed under
field-free conditions. The laser pulse length is not relevant as a
fixed temporal error. The requirements of the high voltage pulse
are firstly an electric field reaching a stable value before the ions
leave the ion source and secondly a very stable and reproducible
pulse shape. Eventual short modulations such as short spikes are
not relevant as long as they are well reproducible. This is also
valid for the rising edge of the HV-pulse. A rising edge of
50 nsec does not mean a temporal error of 50 nsec. It is the
reproducibility of this edge which makes the temporal error.
With the same instrument as in Figure 12, a flight time peak
width of 3.6 nsec has been achieved despite a laser pulse length
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
of 10 nsec and HV-pulse rising edge of 50 nsec. A further
measure, namely the increase of flight times by decrease of ion
kinetic energy, finally allowed a mass resolution of
R50% ¼ 20,000 for trimethylbenzene (120 au) (Boesl, Weinkauf,
& Schlag, 1992). This further measure in detail was the
reduction of ion kinetic energy from 700 to 220 eV resulting in
an ion flight time of 150 ms for mass 120 instead of 70 ms. If
fixed time errors are dominating Dt then longer flight times will
result in an increase of mass resolution due to R50% ¼ 1/2 t/Dt.
One way to achieve longer flight times by smaller ion kinetic
energies is to accelerate the ions with high electric fields in the
first stage of the ion source and decelerate them in the second
stage. This reduces the influence of initial ion kinetic energies Ui
such as generated by space charge. The compensation of energy
incertitude (due to spatial and pseudo-spatial distributions) then
happens in the ion reflector.
Pulsed high voltage ion sources even allow combination
of time-of-flight mass spectrometry with long-term or even
continuous ionization processes such as electron ionization.
A mass resolution of R50% > 15,000 has been observed for
2,4,6-tris-pentadecafluoroheptyl-1,3,5-triazine with a mass of
866 au in a reflectron with gridless ion reflector, high voltage
pulses applied to ion source electrodes, and electron ionization
(Grix et al. 1988). Long flight times of 800 ms have been
achieved by a very long field-free drift region of xD ¼ 800 cm
(qUion ¼ 900 eV) instead of small ion energy as in the former
example.
There is a further advantage of pulsed ion sources. Slow ion
beams, formed in external ion sources, can be directed into the
first stage of a pulsed time-of-flight ion source. Thereby ion
beam axis and time-of-flight ion source (and thus ion extraction
direction) are perpendicular to each other. A pulsed electric field
then will cut cylindrical ion clouds out of the slow ion beam and
accelerate them in direction of ion reflector. At least after the
last ion has reached the ion detector (typically 100 ms), the next
ion cloud can be extracted out of the primary ion beam thus
allowing a repetition rate of larger than 10 kHz. Assuming ion
beam velocities of 10 cm/100 ms (e.g., M ¼ 100 au; qUion ¼ 2
eV) and extracted ion clouds with a diameter of 1 cm duty
cycles of 1–10 are imaginable. Such a perpendicular arrange-
ment of primary ion beam and axis of time-of-flight mass
analyzer are known as Q-TOF (Krutchinsky et al., 1998; Chen
et al., 1999).
Pulsed ion extraction is also used in ToF-MS with MALDI
ion sources for high resolution investigation of large biomole-
cules (Colby et al., 1994; Vestal, Juhasz, & Martin, 1995). A
typical feature of MALDI is that Dx is minimal (desorption from
a well-defined surface) but Dv may be large. Very high electric
fields in the ion source (in the range of kV/mm) keep the turn-
around time small, delayed pulsed ion extraction converts initial
DUi into an initial spatial distribution Dx which can be corrected
for. Ion source space focus SF is shortly behind ion source. The
compensation of ion source spatial incertitude is achieved by an
ion reflector.
4. Large Deceleration Field (b > a)
There exists an alternative to gridless ion reflectors to solve the
problem of ion scattering at the ion reflector meshes. The depth
b ¼ xS of the decelerating field, which is the first field ions
experience when entering the ion reflector, has been assumed to
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be very short, e.g., 2 cm. This allowed several simplifications of
formula (see Eqs. (20) and (21)), easier handling of the
reflectron and a relatively short ion reflector. However, this is
only possible at the expense of large electric fields which
induce large scattering angles (see Eq. (24)). Increasing b ¼ xS
substantially will reduce the scattering problem to a great extent.
A mass resolution of R50% ¼ 22,000 for clusters of more than
800 cesium atoms with masses of over 110,000 au has been
achieved in such a way allowing the resolution of single oxygen
adducts (Bergmann, Martin, & Schaber, 1990). The reflectron
used was specified by xD ¼ 500 cm, b ¼ xS ¼ 29 cm and thus
b > a ¼ xR .
5. Laser Ionization With Short Laser Pulses in the
Picosecond or Even Femtosecond Range
Using laser ionisation with short laser pulses solves two
problems at once. At one hand, fixed time spread due to laser
pulse length does not play are role anymore. On the other hand,
space charge effects are strongly reduced without loss of
ionization efficiency. The pulse energy is considerably smaller
than for nanosecond lasers due to the much shorter pulse length.
This gives rise to much smaller ion numbers per laser pulse
and therefore smaller space charges. Nevertheless, the peak
intensities in pico- and particularly in femtosecond laser pulses
are larger than for nanosecond laser pulses. This enhances
ionization efficiency of multiphoton processes significantly and
ion numbers do not drop by a factor of 103 or even 106 if simply
laser pulse lengths are considered. In addition, the smaller ion
numbers per pulse are compensated by high repetitin rates in
the kHz range and above. This has to be compared to some
20 Hz which is typical for nanosecond lasers. A nice example is
the mass resolution of 2,000 in a 30 cm short linear time-of-
flight mass spectrometer using laser pulses with 170 fsec pulse
length (Lehmann, Ram, & Janssen, 2012). Even mass resolution
of 4,000 and higher are observed for xenon and its isotopes
(Vredenborg, Roeterdink, & Janssen, 2008).
VII. SOME INSTRUMENTAL AND EXPERIMENTAL
OPTIONS OF TIME-OF-FLIGHT MASS ANALYZERS
In the following, some experimental possibilities are presented
which may be realized in home-built linear or reflectron-type
time-of-flight mass spectrometers.
A. Tandem-MS
In addition to their ability to provide time-of-flight mass spectra
with high mass resolution reflectrons have a further intrinsic
feature: the option of so-called tandem-mass spectrometry
(Boesl et al., 1989a; Weinkauf et al., 1989; Beussman et al.,
1995; Giannakopulos et al., 2002). Tandem-mass spectrometry
allows selective detection of fragment ions formed at metastable
decay or secondary excitation of precursor ions. Metastable
decay occurs when the excess energy of a precursor ion above a
fragmentation threshold is small. The fragmentation process
may then be so slow that it happens far away from the point of
ion formation either in the acceleration region of the ion source
or even in the field-free drift region. In a linear time-of-flight
mass analyzer, this gives rise to either a long slope of fragment
ion mass peaks to the high mass side (formation in the ion
source) or even a fragment ion peak hidden under its precursor
ion peak. The reason for that is that fragmentation in the field-
free drift region will result in equal velocities of mother and
daughter ion. A corresponding hypothetical mass spectrum is
displayed in Figure 13a. Fragment ions formed by secondary
excitation (e.g., by collisions with gas molecules or by a second
delayed laser pulse) behave in the same way.
Mass spectra due to metastable decay or delayed fragmen-
tation behave quite differently in reflectrons (Boesl et al., 1982).
This is because fragmentation far away from the point of ion
formation results in a reduced ion kinetic energy of the
corresponding fragment ions as compared with prompt ions.
Thus fragment ions formed in the field-free drift region have to
share the original precursor ion kinetic energy with its neutral

FIGURE 13. Hypothetical mass spectra of fragment ions taken in a linear (a) and a reflectron time-of-flight
spectrometer (b–d). The fragment ions are formed at prompt (FIþ) or metastable decay (FAþ, FDþ) of precursor
ions Mþ. (FIþ: formation at point of ionization, FAþ: in the acceleration region, FDþ: in the field-free drift region).
The reflectron is able to compensate the reduced ion kinetic energy of fragment ions in case (b), but is not so in
case (c). A detuning of the ion reflector potentials by increasing the voltage at the reflector end plate (case (d)) will
shift the FDþ peak toward the precursor ion peak Mþ. Very high end plate voltages will result in very short
distances xR simulating a linear ToF-situation and giving rise to linear ToF mass spectra like in (a).

100 Mass Spectrometry Reviews DOI 10.1002/mas


counterpart. Due to conservation of momentum they end up with
Ukin(FDþ) ¼ Ukin(Mþ) MF/M with the fragment ion mass MF and
the precursor ion mass M. In contrast to linear ToF-MS,
reflectrons are able to compensate this difference in ion kinetic
energy and ions formed at meatastable or delayed fragmentation
will appear at the right flight time corresponding to their mass
(see Fig. 13b) as long as the energy difference DU ¼ Ukin(M+) 
Ukin(FDþ) is in the acceptable range (see Fig. 6). If this is not the
case then mass spectra as shown in Figure 13c will be obtained.
The reason for this is that fragment ions FDþ formed in the field-
free drift region with a too small ion kinetic energy will already
be reflected in the first ion reflector stage and therefore appear
too early at the ion detector.
Mass spectra caused by metastable or delayed decay are
one of the most important sources of information about
molecular structure which is frequently used in molecular
research as well as in analytical chemistry (deHoffmann &
Stroobant, 2007; Gross, 2011). Even UV- or IR-spectroscopy on
molecular ions can be performed using the techniques of
tandem-ToF-MS. Molecular ions are formed and preselected in
the first step while secondary excitation with tunable UV- or IR-
lasers cause fragmentation after resonant excitation (Willey
et al., 1991; Boesl, 1999). One way to realize the tandem-MS
feature of reflectrons is illustrated in the top part of Figure 14.
While laser 1 is responsible for ion formation, laser 2 excites
preselected molecular ions. This is achieved by focusing it into
the space focus of the ion source/ion reflector and firing it at a
delay time to laser 1 which exactly is the flight time of the ion of
interest to the space focus. Secondary fragment ions then are
detected by the ion reflector, e.g., by firing laser 2 only every
second pulse of laser 1 and measuring difference mass spectra
or by using the method described in Section B. Notice that a
whole tandem mass spectrum is obtained for every single pulse
of laser 2.
Unfortunately, there is a major drawback of using reflec-
trons for tandem-MS. Reasonable compensation of ion energy
incertitude is restricted to a relative range DU/U < 25%. As an
FIGURE 14. Upper part: realization of tandem-MS in a reflectron using delayed excitation and fragmentation of
preselected ions by a second laser. Lower part: postacceleration of ions to overcome the acceptance of energy
difference DU < 0.25 U in conventional reflectrons.
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
example let us consider the benzene radical cation C6H6þ
(M ¼ 78 au) which may have an ion kinetic energy of qU ¼ 500
eV and its fragment ion Cþ (M ¼ 12 au). If this fragment ion is
formed in the field-free region then its ion kinetic energy is
qUF ¼ qU MF/MV ¼ 500 (12/78) eV ¼ 77 eV due to conservation
of momentum. This corresponds to a qDU of 423 eV or a DU/U
of 85% and exceeds the range of acceptance of reflectrons by
far. One possibility is to reduce all potentials of the ion reflector
step by step by a certain amount (e.g., 20%) and taking a
tandem-MS for each step. Then, all partial mass spectra are
added up to a total mass spectrum. This approach has been
applied in the early days of peptide sequencing by tandem-MS
with reflectrons (Spengler, Kirsch, & Kaufmann, 1991). A more
elegant way is post-acceleration as illustrated in the lower part
of Figure 14. A shielded part of the field-free drift region
including the space focus point SF is shifted by a considerable
amount of potential (e.g., by 4,000 V). It is reasonable to do this
in a pulsed way, e.g., for keeping the potentials in the ion source
as low as possible.
Since the secondary, delayed fragmentation happens before
the post-acceleration from 4,000 V to 0 V all ions (precursor as
well as secondary fragments) gain an ion kinetic energy of
4,000 eV. In our scenario of Cþ formation out of C6H6þ ions,
this results in a relative energy difference of DU/U ¼ 423/
4,500 ¼ 9,4% which easily can be corrected for in the space
focus of the ion reflector (Boesl et al., 1990a,b).
B. Movable Reflector Endplate
A very useful instrument to measure ion kinetic energies, to
detect product ions from metastable decay, or to select fragment
ions formed at delayed excitation from prompt molecular and
fragment ions is the movable reflector endplate (Boesl et al.,
1989b). This is a second final ion reflector electrode e2 which is
mounted in such a way that it can be moved toward the two front
grid electrodes f1 and f2 on the axis of the ion reflector (see
Fig. 15). During this movement, the high voltage applied to this
101
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FIGURE 15. Upper part: ion trajectories a of low energy ions (e.g., products of metastable decay) and ion
trajectories b of high energy ions (e.g., prompt ions). On the right side: exemplary mass spectrum of radical
benzene cation and two products due to metastable H and H2-loss. Lower part: Movable end electrode e2 has been
shifted and the high voltage HVe2 reduced for constant reflecting field Eref so that high energy ions hit the electrode
and disappear from the mass spectrum as seen on the right hand side. f1, f2: front electrodes, e2, e1 end electrodes
of the ion reflector.

electrode is reduced so far that the electric field between
electrode e2 and f2 stays constant and is equal to electric field
for full energy incertitude compensation. This can be done in a
stepwise way. For the above scenario with xD ¼ 80 cm and a
distance of 2 cm between electrode f2 and f1, energy compensa-
tion would be obtained for HVf2 ¼ 2/3 U and a penetration depth
xR of ions into the reflecting field ER of xR ¼ xD/10.6 ¼ 7.5 cm
(see Eq. (21)). Let us further assume a distance of 10 cm
between electrode f2 and e1 and an original ion kinetic energy of
500 eV. The potential at electrode f1 would then be 0 V, at
electrode f2 333.3 V, at the point of ion return 500 V, and at the
endplate e1 555.6 V. The electric field ER which has to be kept
constant then is 22.2 V/cm. A motion of 1 mm of the movable
endplate e2 would then require a reduction of potential HVe2 by
2.2 V. This is in the range of the energy difference of 6.5 eV
between the product C6H5þ from metastable decay of C6H6þ
and promptly formed ions.
In Figure 15, two different positions of the second end plate
are displayed. In the upper case, ion trajectory a of low energy
ions (e.g., fragment ions from metastable decay) and trajectory b
of high energy ions (e.g., prompt ions) are not affected by the
second endplate and both reach the ion detector. In the lower
case, the endplate e2 is moved so far toward the front electrodes
and its potential is so much lowered (HVe2 < U) that the high
energy ions hit the endplate and disappear from the mass
spectrum. Exemplary mass spectra of benzene radical cation
C6H6þ are shown on the right hand side of Figure 15. It is known
that 2-photon ionization with 253 nm laser light results in
efficient metastable decay of C6H6þ if the laser light intensity is
large enough and a third photon is absorbed within the parent
ion (Boesl et al., 1982). C6H5þ and C6H4þ are products of this
3-photon excitation. A motion of the endplate e2 to a position
with HVe2 < 500 V but >494 eV then results in the disappear-
ance of the parent ion and its 13C1-isotopomer from the spectrum
(see lower mass spectrum in Fig. 15).
It is important to use gold-plated surfaces of the movable
endplate to avoid surface charges due to islands of oxides which
easily could cause potential differences in the low Volt range. If
this is prevented, movable end plates can even be used to
measure ion kinetic energies U and thus determine the spatial
ion distribution in the ion source more accurate or detect kinetic
energy released at fast parent ion decays. A further option of the
movable end plate is to use a grid instead of a solid plate and to
position a second ion detector in the center of endplate e1. This
allows to measure fragment ions from metastable decay and
parent ions synchronously (although the latter with reduced
mass resolution) for every single laser shot.
C. Further Options
There exist many further options some of which here are
mentioned only shortly. The reader is referred to the cited
literature for further details. All these examples illustrate how
versatile time-of-flight mass spectrometry can be; they may
encourage all those who want to experiment with mass
spectrometry: hardware changes—at least at home-built instru-
ments—are definitely feasible.
1. Transit Ion Detector
The first two options are extensions for tandem-MS. One is the
so-called transit ion detector (Drechsler et al., 1994). For some
applications (e.g., secondary delayed excitation or deposition of
ions on surfaces), it is useful to measure a mass spectrum
beforehand. For this reason, a very thin wire, which is oriented
perpendicularly to the ion trajectories, is mounted in the way of
the ion beam in the field-free drift region. Only few percent of
the ions hit this wire and give rise to secondary electrons. These
are extracted perpendicularly to wire and ion beam and detected
by a channeltron or multichannelplate detector. The ion beam

102 Mass Spectrometry Reviews DOI 10.1002/mas


itself is nearly not affected. This wire may be placed in the space
focus of the ion source or even replace the final ion detector so
that the ions are available for further experiments. The whole
transit-detector assembly can be kept small enough to be
mounted into already existing instruments.
2. Mass Selection by Ion Deflecting Grid
For some experiments, it may be necessary to clean the ion
clouds from ions with certain masses or even to leave only ions
of one mass in the ion beam. In time-of-flight mass spectrome-
try, this is usually achieved by two electrodes to which potentials
of same magnitude but opposite sign are applied. The so-formed
electric field is oriented in such a way that the corresponding
force on charges is perpendicular to the ion trajectories and
causes deflection of ions from the ion beam. A selection of mass
ranges is possible by using pulsed high voltages. However, the
selectivity for single masses might be very rough. Here helps a
type of grid deflector (Weinkauf et al., 1989). Again, very thin
wires are used which are mounted parallel to each other in a
distance of about 1 mm. The whole assembly is placed into the
way of the ion beam with the wires perpendicular to the ion
trajectories. A pulsed voltage is applied to all wires such that
neighbored wires have a potential of same size but opposite
sign. Due to the small distances, large deflecting electric
fields are caused even for small voltages. In a short distance
before and behind the whole assembly, the electric fields are
cancelling out (opposite sign of neighbored voltages) and do
not disturb the field-free drift region. Therefore the whole
assembly may be placed in the space focus of the ion source
allowing much higher selectivity of the deflection unit. For
reasonable mass selection, one should design an ion source (or
choose appropriate ion source voltages) whose space focus is
not near to the extracting electrode (as for instance linear ToF in
Fig. 8).
3. Mass Selective Molecular Spectroscopy
A particularly interesting option of time-of-flight mass spec-
trometry is its combination with other spectroscopic techniques
such as UV-spectroscopy or photoelectron spectroscopy. Such
combinations reveal two-dimensional selectivity with great
impact for problems of chemical analysis or molecular research.
Mass-selective UV-spectroscopy or UV-selected mass spectra
performed via resonance enhanced multiphoton ionization
(REMPI) (Boesl, 1991, 1999, 2000) already find broad applica-
tions. For an introduction see for instance (Letokhov, 1987;
Parks & Young, 2001); a recent example of mass selective
molecular spectroscopy is REMPI on bromobenzene (Andrejeva
et al., 2015); a recent overview of application of mass selective
REMPI in chemical analysis (Streibel & Zimmermann, 2014).
The combination of time-of-flight mass spectrometry with
photoelectron spectroscopy is more difficult and mainly used in
fundamental research. There exist two techniques to measure
photoelectron spectra which work in a pulsed way and therefore
go well together with time-of-flight mass spectrometry. One is
based on the flight time, the other on the angular distribution of
electrons; both are correlated to electron kinetic energy. Both
methods are supplying full spectra for every single photoemis-
sion inducing event. For good signal to noise ratio, however, an
averaging over many laser pulses is necessary. They differ from
Mass Spectrometry Reviews DOI 10.1002/mas
TIME-OF-FLIGHT MASS SPECTROMETRY &
stepwise tuning methods by speed, sensitivity, and low depen-
dence on pulse-to-pulse fluctuations and are suited for combina-
tion with mass selection.
4. Mass Selective Photoelectron Spectroscopy
Photoelectron spectra reflect internal energies and thus spectro-
scopic details of molecular kations (photoelectron emission
from neutrals) or neutrals (photoelectron emission from
anions) due to: Ekin(e) ¼ hn  IP  Eint(kation) or Ekin(e) ¼
hn  DE  Eint(neutral), respectively. hn is the energy of the
photon which induces photoelectron emission. IP is the ioniza-
tion threshold, DE the photoelectron detachment threshold
(which equals the adiabatic electron affinity in amount), and
Eint the internal energy of the remaining ionized or neutral
molecule. Eint can be vibrational, electronic, or vibronic
(combination of both) energy. Two ways of realizing mass
selective photoelectron spectroscopy exist. Which one is
applicable depends on whether neutral or negatively charged
molecules are excited.
In the latter case, photoelectron emission takes part at
charged species: hn þ A ! e þ N which is therefore also
called photoelectron detachment spectroscopy. Ions as precursor
have the advantage that mass selection prior to photoexcitation
is easily possible, e.g., by focusing a laser beam into the space
focus of the ion source. The photoelectrons are extracted
perpendicularly to the ion beam into a time-of-flight analyzer or
are recorded in-line with the ions by an imaging ion/electron
detector. Mass selected photoelectron detachment spectra of
diverse molecular ions or fragment ions are possible by delaying
the photodetaching laser pulse with respect to the ion formation
(Metz et al., 1990; Arnold, Xu, & Neumark, 1995; Boesl &
Knott, 1998).
The more common case of photoelectron spectroscopy is
photoelectron emission from neutral species: hn þ N ! e þ
Kþ. The problem here is that mass selection on neutral
molecules is not possible. In this case so-called photoion
photoelectron coincidence spectroscopy is applied (Brehm &
von Puttkammer, 1967; Baer, Booze, & Weitzel, 1991). The ion
yield per ionization pulse is reduced to less than one. In this
case, each electron and electron spectrum can be correlated to a
molecular ion. The very low sensitivity of single ionization
events may be compensated by a high pulse repetition rate.
Modern laser systems allow working in the 10 kHz range. Again,
electron kinetic energy analyzing can be performed by measur-
ing electron flight times where the photoelectron flight time
analyzer is arranged in line but in opposite direction regarding
the ion flight time analyzer. A very nice arrangement is displayed
in Figure 16 where electron angular distribution is recorded for
photoelectron spectroscopy (Vredenborg, Roeterdink, & Jans-
sen, 2008; Lehmann, Ram, & Janssen, 2012). It is convincing by
its compactness using only one field-free drift region and one
ion/electron detector.
In Figure 16, photoelectron spectroscopy is based on the
fact that the electron cloud formed at photoionization spreads
out due to the photoelectron velocity distribution (Chandler &
Houston, 1987). The two-dimensional image of the angular
distribution supplied by the ion/electron detector is the integral
of the three-dimensional angular photoelectron distribution over
the direction of electron extraction. Since the electrons are
considerably faster than the ions the recording of photoelectron
103
& BOESL

FIGURE 16. Combination of time-of-flight and photoelectron spectrometry in photoion photoelectron

coincidence spectroscopy. The high voltages are pulsed in such a way that the electron trajectories are optimized
for imaging their angular distributions on the two-dimensional detector surface. Photoelectrons are recordedt at
times t < 200 ns after the laser pulse, while the mass spectrum of the much slower ions is measured at t > 200 nsec.

spectra is finished after 200 nsec. The spectrometer is switched where DtDM ¼ 1 is the difference of neighbored mass peaks with
from photoelectron to photoion recording mode after this time DM ¼ 1. Then one can formulate:
by using pulsed high voltages applied to the electrodes. The
amplitudes of the voltages are optimized for electron angular M 1 t DtDM¼1
R50% ¼ ¼ ¼M ðA4Þ
distribution imaging and mass spectrum with good resolution, DM 2 DtFWHM DtFWHM
respectively.

VIII. APPENDIX
B. Acceleration Time tA2 in the Second Stage of a
Two-Stage Ion Source
A. Mass Resolution Determined From Time-of-Flight tA2 may be described in the following illustrative way. At first,
Spectrum we determine the hypothetic flight path xU within an electric
field EA2 (¼UA2/xA2) so that the ions with mass M would reach a
From the relations kinetic energy qU. This gives an acceleration flight time tA2(1).
rffiffiffiffiffi rffiffiffiffi rffiffiffiffiffi For xU one gets xU ¼pðffiffiffiffiffiffiffiffiffiffiffiffiffiffi
U=U A2ffi ÞxA2 . The corresponding flight
pffiffiffiffiffi
M dt 1 1 1 11 M 11 time is tA2 ð1Þ ¼ xU M=EA2 2C. Then the hypothetic flight
t¼x C and ¼ x pffiffiffiffiffi C¼ x C¼ t
U dM 2 M U 2M U 2M path xUA1 within the same electric field EA2 is determined so that
the ions with mass M would reach the “starting” kinetic energy
UA1. This gives an acceleration flight time tA2(2). For xUA1 one
gets xUA1 ¼ ðU A1p =U A2 ÞxA2 ffi with the corresponding flight time
follows pffiffiffiffiffiffiffiffi ffiffiffiffiffiffiffiffiffiffiffiffiffiffi
tA2 ð2Þ ¼ xUA1 M=EA2 2C. The time for acceleration in the
dt 1 dM M 1 t second stage is then tA2 ¼ tA2 ð1Þ  tA2 ð2Þ. Putting everything
¼ or ¼ ðA1Þ
t 2 M DM 2 DtFWHM together gives:

rffiffiffiffiffiffiffiffi
M 1 t pffiffiffiffiffi pffiffiffiffiffiffiffiffi
M
R50% ¼ ¼ ðA2Þ tA2 ¼ xU  xUA1 2C
DM 2 DtFWHM EA2

Hereby, DM and DtFWHM are the full widths at half- rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffirffiffiffiffiffiffiffiffi
U U A1 M
maximum of mass and flight time peak, respectively. DtFWHM ¼ xA2  xA2 2C
U A2 U A2 EA2
corresponds to the flight time incertitude Dt. Another formula-
tion for R50% follows from pffiffiffiffi pffiffiffiffiffiffiffiffiffi x pffiffiffiffiffi
A2
¼ U  U A1 M 2C
M 1 t M 1 t U A2
¼ and DM ¼ 1 ) ¼ or t ¼ 2MDtDM¼1
DM 2 Dt 1 2 DtDM¼1 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffi
M
ffi
ðA3Þ respectively ¼ xA1 EA1 þ U A2  xA1 EA1 2C ðB1Þ
EA2

104 Mass Spectrometry Reviews DOI 10.1002/mas

 TIME-OF-FLIGHT MASS SPECTROMETRY &

C. Relation of R and Geometric Parameters a, b, c for a Solving this equation results in Equation (22):
Second Order Space Focus
To calculate this relation, it is feasible to multiply Equation (15) 1  
by Ua1 and then set it equal to Equation (16). The terms a¼ b þ cR3=2 resp:
R1
containing Ua3/2 cancel each other. Multiplying by U2 and
using U/Ua ¼ R and U/Ub ¼ R/(R  1) gives   !
c  2b c  2b 3=2
a¼ bþc ðD1Þ
2c þ 2b 3c
  3=2   1=2
a b 1 b c1 1 1
0¼  þ 
Ua Ub Ua Ub 2 U U Ua

b 1 c1 1 b 1 3c 1 E. Dwelling Time of Ions in the Ion Reflector

)  ¼ 
Ub Ua 2 U Ua Ub U 2 U2
1. Rough estimation (b ¼ 0)
U U cU U 3c
)b  ¼b   3=2
Ub Ua 2 Ua Ub 2 1 1
b ¼ 0 ! R ¼ 3 ! a ¼ 1=2c  ¼ 0:096c ¼ c
  3 10:4
U U c U 3c
)b 1 ¼ 
Ub Ua 2 Ua 2
U
and with U a ¼ U  U b ¼
R
R1 c 3
)b ¼ bR ¼ R  c
1  1=R 2 2
rffiffiffiffiffiffiffiffiffi rffiffiffiffiffi
M 2c pffiffiffi M
tRef ¼ 2a R C¼ 3 C ¼ 0:333 tc
U 10:4 U
3=2c 3c
R¼ ¼
c=2  b c  2b 2. More detailed estimation (b ¼ 0.025 c)

 
3 0:95 1 0:95 3=2 1
D. Geometric Parameters of a Two-Stage Ion Source R¼ !a¼ cð þ ¼ 0:094c ¼ c
0:95 2:05 40 3 10:6
With Second Order Space Focus
Inserting Equation (18) into Equation (15) results in a general
geometrical relation of a, b, and c for a second order space focus. 2 pffiffiffi
and tRef ¼ R tc ¼ 0:335tc
For easy reformulation, Equation (15) is multiplied by Ub Ua1/2 10:6
and relation Ub ¼ U  Ua is used:
and tb : U b ¼ ð1  1=RÞU < U !
rffiffiffiffiffiffi rffiffiffiffiffiffi
Ub Ua c Ub Ua rffiffiffiffiffi
0¼a bþb  M
Ua U 2U U tb > 0:025c C ¼ 0:025 tc
U
rffiffiffiffiffiffi rffiffiffiffiffiffi rffiffiffiffiffiffi
Ub Ua c Ua c Ua Ua
¼a bþb  þ
Ua U 2 U 2U U tIR ¼ 0:360 tc ðe:g:; for b ¼ 2 cm; c ¼ 80 cmÞ

Because of 1=R ¼ c2b 3. More detailed estimataion (b ¼ 0.05 c)

3c or 2b  c ¼ 3c=R ¼ 3c U (see
Ua

Eq. (18)), one obtains:

 3=2
rffiffiffiffiffiffi rffiffiffiffiffiffi R¼
3
!a¼
0:9 1
cð þ
0:9
¼ 0:081 c ¼
1
c
Ub 2b  c U a c U a U a 0:9 2:05 40 3 12:3
0¼a bþ þ
Ua 2 U 2U U

rffiffiffiffiffiffi
Ub Ua Ua 2 pffiffiffi
¼a bc ¼ aðR  1Þ  b  cR3=2 and tRef ¼ R tc ¼ 0:30tc
Ua U U 12:3

Mass Spectrometry Reviews DOI 10.1002/mas 105

& BOESL

rffiffiffiffiffi
M Difference Dxin of ion trajectories a and b:
and tb : U b ¼ ð1  1=RÞU < U ! tb > 0:05c C ¼ 0:050 tc
U
Dxin ¼ Dyin sin a ¼ xD1 Da sin a
tIR ¼ 0:350 tc ðe:g:; for 4 cm; c ¼ 80 cmÞ
Width Dyout of ion beam entering the ion reflector:
F. Effects of Ion Beam Divergence (Detector Surface in Dyout ¼ (xD1 þ 2(2xR)) Da
Position A)
1. Time error arising inside the reflecting field Eref (see Fig. 9) Difference Dxout of ion trajectories a and b:

Relevant velocity component: vk ¼ v  cos a Dxout ¼ Dyout sin a ¼ (xD1 þ 2(2xR)) Da sin a
Relevant kinetic energy: U k ¼ U  cos2 a Same assumption for auxiliary trajectory as above.
Relevant kinetic energy in the reflecting field Eref:
Difference in path length in the field free drift region of
U k ref ¼ 1=3 U  cos2 a trajectories a and b:
Relevant velocity in the reflecting field Eref:
Dx ¼ Dxout  Dxin ¼ 2(2xR)) Da sin a
pffiffiffiffiffiffiffiffi
vk ref ¼ 1=3 v  cos a Estimation:
Dwelling time in the reflecting field: Dx ¼ 1/10.5 (1/2 xD) 0.012 sin 4˚ ¼ 0.065 cm
rffiffiffiffiffi rffiffiffiffiffiffiffiffi
M
2C with xR from Eref xR ¼ 1=3U  cos a
2
tref ¼ 2  xR 106
U Dt ¼ 0:065 0:72 msec ¼ 20 nsec or Dt ¼ 10 nsec:
600
xR is the ion penetration depth into the reflecting field. Please notice: trajectory a is shorter than trajectory b and
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
M therefore reveals shorter flight time.
tref ¼ 2  1=3 U  cos a=Eref 
2
2C
1=3 U  cos2 a 3. Summary of effects (1) and (2):
sffiffiffiffiffiffiffiffiffiffiffiffiffi
M Flight time of trajectory a is by 34 ns shorter than that of
¼ 2  1=3 U=Eref  2C  cos2 a trajectory b.
1=3 U

dtref =da  tref ðsin aÞ cos a  1 for small a
Dtref ¼ tref  sin a  Da
Notice: larger angles a (e.g., trajectory a) result in shorter
dwelling times tref.
Estimation:
Ion beam divergence:
Da  Ddet =ðxD þ 2ð2xR ÞÞ  2=180 ¼ 0:012 rad
Ddet: diameter of circular detector surface ¼ 2 cm;
xD þ 2ð2xR Þ: auxiliary ion trajectory length if no deceleration
and no ion reflection would occur (see dotted ion trajectories
in Fig. 9).
xD ¼ 160; xR ¼ 1/10.5 (1/2 xD) (see Eq. (21)).
tref ¼ 0.35/1.35 ttotal from
ttotal ¼ (1 þ 0.02 þ 0.33) 2 c (M/U)1/2 C (see Eq. (23))
Dtref =ttotal ¼ 0:35=1:35  sin 4  0:012 ¼ 2:2  104
Dtref  14 nsec or  7 nsec for ttotal ¼ 63 msec:
2. Time error arising inside the field-free drift region xD1 and
xD2 (see Fig. 9)
G. Typical Ion Numbers at Multiphoton Ionization per
ns-Laser Pulse
The ion numbers of 5  104 in the focussed and of 5  103 in the
unfocussed case have been chosen for optimally illustrating the
effect of space charge. That these numbers may easily be
achieved or even largely surpassed in practice will be shown in
the following estimation of ion numbers per laser pulse at
resonantly enhanced multiphoton ionization in the unfocussed
case. We assume an unfocussed laser beam with a diameter of
1 mm and a gas beam with a diameter of 2 mm. The ionization
volume is then roughly Vi ¼ 2 mm3. A partial pressure of
105 mbar in the gas beam is assumed. Furthermore, we assume
a laser pulse with 200 nm wavelength, a pulse energy of
PL ¼100 mJ (equivalent to 1014 photons with 200 nm ) and a
pulse length of tL ¼10 nsec. Considering the laser beam cross
section of roughly sL ¼ 1 mm2 or 0.01 cm2, we obtain a laser
intensity of IL ¼ PL/(tL  sL) ¼ 106 W/cm2 or 1024 photons/
(s cm2). Typical molecular absorption cross sections (weak first
absorption cross section s1) are assumed. For not too high laser
pulse energies per cm2, the first resonant absorption step is not
saturated (s1 IL t << 1) and rate equations can be used to
calculate ion numbers [Mþ] (Boesl, 1991). The solution for two-
step absorption ionization with one resonant intermediate state
is given below:

Width Dyin of ion beam entering the ion reflector:

200 nm photons: NPh ¼ PL/EPh ¼ PL/(hcl) ¼ 1014 for PL ¼ 100 mJ and
Dyin ¼ xD1 Da l ¼ 200 nm.

106 Mass Spectrometry Reviews DOI 10.1002/mas

 TIME-OF-FLIGHT MASS SPECTROMETRY &

1. [M+] = [M] 1/2 σ1 σ2 I2 τ2

typical molecular
2. laser specification
absorption cross sections
σ1 = 10-18 cm2 I = 1024 photons/(s cm2)
σ2 = 10-17 cm2 τ = 10 ns
3. [M+] = [M] 1/2 10-3 in the laser focus
V = 2 mm3, p = 10-5 mbar, T=300K
4.
This is equivalent to 3·108 molecules/mm3
total neutral molecules: [M] = 6·108 molecules
5. [M+] = 3·105 ions per laser pulse

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Ulrich Boesl is former group leader and Professor at the Chair of Physical Chemistry of the
Technical University of Munich. During his postdoctoral research, he developed techniques to
combine time-of-flight mass spectrometry and molecular spectroscopy in Munich, and worked
together with Th. H€ansch on high resolution laser spectroscopy in Stanford/California. His
main subjects of research in Munich were mass-selective molecular spectroscopy and its
application in chemical trace analysis, involving resonance-enhanced multi-photon ionization,
supersonic beam cooling, laser evaporation of large molecules, molecular anion photodetach-
ment, and enantiomer-selective laser spectroscopy. Together with U. Heiz, he gained an
advanced ERC grant on Asymmetric Cluster Catalysis and Chemistry.

Mass Spectrometry Reviews DOI 10.1002/mas 109