Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 711716

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Chemical bonding and electronic structures of microcline, orthoclase

and the plagioclase series by X-ray photoelectron spectroscopy
J. Theo Kloprogge a,, Barry J. Wood b
a
b

School of Earth Sciences, The University of Queensland, St. Lucia, Qld 4072, Australia
Centre for Microscopy & Microanalysis, The University of Queensland, St. Lucia, Qld 4072, Australia

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 XPS showed the effect of symmetry

on Si 2p and Al 2p for microcline and

orthoclase.
 XPS showed the effect of coupled
substitution on Si 2p, Al 2p and O 1s
in plagioclase.
 The Si 2p, Al 2p and O 1s binding
energies decrease from albite to
anorthite.
 The bonding character for microcline
is more covalent than Al2O3 but less
than SiO2.
 Plagioclase shows two distinct
bonding characters comparable to
SiO2 and Al2O3.

a r t i c l e

i n f o

Article history:
Received 30 May 2014
Received in revised form 11 August 2014
Accepted 24 August 2014
Available online 10 September 2014
Keywords:
Microcline
Orthoclase
Plagioclase
X-ray photoelectron spectroscopy
Albite
Anorthite

a b s t r a c t
A detailed analysis was undertaken of the X-ray photoelectron spectra obtained from microcline,
orthoclase and several samples of plagioclase with varying Na/Ca ratio. Comparison of the spectra was
made based on the chemical bonding and structural differences in the Al- and Si-coordination within
each specimen. The spectra for Si 2p and Al 2p vary with the change in symmetry between microcline
and orthoclase, while in plagioclase an increase in AlOSi linkages results in a small but observable
decrease in binding energy. The overall shapes of the O 1s peaks observed in all spectra are similar
and show shifts similar to those observed for Si 2p and Al 2p. The lower-VB spectra for microcline and
orthoclase are similar intermediate between a-SiO2 and a-Al2O3 in terms of binding energies. In the plagioclase series increasing coupled substitution of Na and Si for Ca and Al results in a change of the overall
shape of the spectra, showing a distinct broadening associated with the presence of two separate but
overlapping bands similar to the 21 eV band observed for quartz and the 23 eV band observed for corundum. The bonding character for microcline and orthoclase is more covalent than that of a-Al2O3, but less
than that of a-SiO2. In contrast, the plagioclase samples show two distinct bonding characters that are
comparable with those of a-SiO2 and a-Al2O3.
2014 Elsevier B.V. All rights reserved.

Introduction

Corresponding author. Tel.: +61 7 3365 2366.

E-mail address: j.kloprogge@uq.edu.au (J.T. Kloprogge).
http://dx.doi.org/10.1016/j.saa.2014.08.120
1386-1425/ 2014 Elsevier B.V. All rights reserved.

Feldspars belong to the most abundant minerals in the earths

crust and form a major component in almost all igneous rocks
and many metamorphic rocks. The feldspar minerals are

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J.T. Kloprogge, B.J. Wood / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 711716

aluminosilicates whose structures are composed of corner sharing

AlO4 and SiO4 tetrahedra linked in an innite three-dimensional
array (Fig. 1). Charge balancing cations such as Na+, K+ and Ca2+
with ionic radii larger than 1.0 occupy large, irregular cavities
in the tetrahedral framework [1].
Reactions comprising feldspars are of major importance in the
environment, inuencing geochemical cycles in different ways.
Feldspar dissolution has been extensively studied in the laboratory,
in order to reproduce and gain a better understanding of the processes involved in weathering and clay formation as seen in
the environment. A good review of this topic is given by Chardon
et al. [2]. XPS has been extensively used to study the changes in

Fig. 1. Ball and stick models of (a) albite and (b) microcline, and polyhedral models
of (c) albite and (d) microcline).

feldspar surfaces. Early studies on feldspar dissolution have indicated that under low temperature and pressure conditions (from
room temperature up to 100 C, 1 atm. pressure, pH from 2 to 8),
no leached layer is detectable and the dissolution appears to be
stoichiometric. This advocates a surface reaction mechanism
instead of one comprising the formation of a leached layer
depleted in alkali ions. More recent studies have focussed on the
dissolution of feldspars at higher temperatures (>200 C) and pressures (>300 bars). The existence of a leached layer up to 100 nm
thick (depending on the particular feldspar mineral studied), and
depleted in Al, Na and O but enriched in Si, has been detected by
XPS. The top few atomic layers are drastically depleted in Al and
Na, emphasizing the incongruent nature of the dissolution. However, the real strength of XPS measurements is in their capacity
to give both species information and elemental composition of
the material at the surface [2].
Other studies focussed on the absorption of other compounds
on the surfaces of feldspars. Vidyadhar et al. [3] for example looked
at the absorption of long-chain primary amines on albite and
microcline with, among other techniques, XPS. Pelte et al. [4] studied the changes in cadmium removal by heat treated feldspars. The
XPS spectra of an albite and an orthoclase were compared with
their reference samples in good agreement with XPS spectra collected by other authors [5]. The binding energies of O 1s, Si 2p 3/
2 and Al 2p 3/2 photoelectron peaks, located respectively at
532.8 0.2 eV, 102.6 0.2 eV and 74.1 0.2 eV are characteristic
of the chemical environments which were reported for these three
elements in silica, alumina oxides and tectosilicates [5,6]. Graveling et al. [7] examined the adsorption of partially hydrolyzed polyacrylamide (HPAM) to kaolinite, feldspar, and quartz. The survey
XPS spectra of the HPAM-free control minerals showed bands in
the O ls, Si 2p, A1 2p, and C ls regions. Again, additional peaks in
the C ls and N ls regions appeared following treatment with HPAM.
When the HPAM level was progressively raised for quartz, kaolinite, and feldspar, the O ls signal from the minerals was so large that
the weak signal from the polymer was masked. Consequently, the
intensity of the N ls peak was used to track levels of surface-bound
HPAM. Unfortunately, in all of these studies no attention has been
paid to the effects of the crystal structures of the feldspars studied
and how changes in these structures affect the high resolution Si
2p and Al 2p spectra.
The differences in the chemical bonding and electronic structures of the feldspars are fundamental to the understanding of
their thermodynamic properties and stability relations. X-ray
photoelectron spectroscopy (XPS) is a technique to probe the
chemical bonding of specic elements. However, application of
the XPS technique to minerals, like the feldspars, can be difcult
due to sample charging during the analysis. The advantage of XPS
over Auger is that in XPS the area under the photoelectron peak
(which is used to calculate Atom %) is easily estimated whereas
in Auger the peakpeak of the differential of the peak is used.
This pp of this differential is a function of the peak shape which,
with Auger, can change signicantly form compound to compound of the same element. Also, for Auger the surface needs
to be reasonably conducting and Auger on insulators poses problems. There is also sample degradation which can be problem
with the highly focused electron beam uses for Auger emission.
Degradation by the soft Al K alpha X-rays used for XPS is only
experienced by a very few compounds. The only advantage for
Auger is you can get analysis from a very small area as it uses
a focussed electron beam as in a SEM. Detailed analyses of photoelectron spectra obtained from aluminosilicate glass have been
reported [8,9]. In glass form, however, Al and Si polyhedra are
all corner linked, therefore the present study can give further
insight into the chemistry and electronic structure of the potassium, sodium and calcium feldspars.

J.T. Kloprogge, B.J. Wood / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 711716

A detailed study has been undertaken using X-ray photo electron spectroscopy of microcline, orthoclase and plagioclase to
probe the differences in their chemical bonding, and compared
their electronic structures with those of a-SiO2 (quartz) and
a-Al2O3 (corundum), which was described in earlier work; [10]
using proper charge compensation techniques.
Experimental
Mineral samples
All feldspar samples used in this study formed part of the geological reference collection of the School of Natural Resources,
Queensland University of Technology. The localities of the samples
were unknown. All samples were checked for purity by X-ray diffraction and electron-microprobe analysis (EMP) prior to the XPS
analysis.
XPS analysis
The depth beneath the sample surface probed by XPS analysis is
determined by the inelastic mean free path of the electrons for a
given energy, material, and angle of emission of those electrons
from the surface. Typically, effective escape depths are between
4 and 40 , thus making XPS a very good probe of the surface environment. For nely ground powders though, this approximates a
bulk analysis. The feldspars were freshly grinded using a mortar
and pestle. The samples were analyzed in freshly powdered form
in order to prevent surface oxidative changes. Typical duration
for the powders being exposed in air (prior to evacuation in the
sample load-lock chamber) was less than 5 min.
Prior to the analysis the samples were out-gassed under vacuum (appr. 5  10 7 torr) overnight in the standard Kratos load
lock system at room temperature. The XPS analyses were performed on a Kratos AXIS Ultra with a monochromatic Al X-ray
source at 150 W. The base vacuum in the analysis chamber during
XPS measurements is <5  10 9 torr. Each analysis started with a
survey scan from 0 to 1200 eV with a dwell time of 100 ms, pass
energy of 160 eV at steps of 1 eV with 1 sweep. For the high resolution analysis the number of sweeps was increased, the pass
energy was lowered to 20 eV at steps of 100 meV and the dwell
time was changed to 250 ms. In the analysis, the absolute value
of the binding energy was calibrated by setting the C(1s) peak
for the adventitious hydrocarbons accumulated on the surface at
284.90 eV.
Band component analysis was undertaken using the Jandel
Peakt software package, which enabled the type of tting function to be selected and allows specic parameters to be xed or
varied accordingly. Band tting was done using a LorentzGauss
cross-product function with the minimum number of component
bands used for the tting process. The GaussianLorentzian ratio
was maintained at values greater than 0.7 and tting was undertaken until reproducible results were obtained with correlations
of r2 greater than 0.995.
The results are compared to those from a-Al2O3 (corundum)
and a-SiO2 (quartz) phases. The binding energies of O(1s) found
in a-Al2O3 and a-SiO2 are 530.7 eV and 533.1 eV, respectively,
which are close to those reported previously (531.2 eV for
a-Al2O3 and 532.8 eV for a-SiO2) [11].
Results and discussion
Fig. 2 shows the survey scans of microcline, orthoclase and the
plagioclase series in the range from 1200 to 0 eV. In agreement
with the XRD results no other minerals are present. A minor

713

amount of advantageous carbon can be observed due surface contamination. Besides the in this study used Si 2p and Al 2p bands
also the Si 2s and Al 2s can be observed around 151 and 117 eV,
respectively.
After adjustment to exclude O and C from both XPS and EMP
analyses the elemental compositions of the feldspar samples agree
reasonably well with electron probe microanalysis, Ca, Si, and Al
being within 2.7% of EMP values and Na within 5.5%. The deviation
in results between XPS and EMP are due to many factors, in particular the algorithms used to convert raw intensities into concentration. XPS analyses may reasonably be compared with each other to
allow concentration variations within samples or between samples
to be determined. Table 1 gives an overview of the chemical analyses based on the XPS results.
Si 2p core-level spectra
Fig. 3 shows the Si 2p spectra obtained for the feldspars in comparison to that of alpha-quartz, SiO2. The Si atoms in all feldspars
are tetrahedrally coordinated to four oxygen atoms and form Si
OSi and SiOAl linkages. Analyses indicate that all the spectra
reasonably fall into a single Gaussian peak within a range of binding energies between 102.45and 102.92 eV (see Table 2), suggesting that the electronic environment around Si atoms in all
feldspars is rather similar but is considerably shifted compared
to quartz (a-SiO2). The second nearest-neighbor Al atoms do have
a signicant inuence on the electronic structure of the tetrahedrally-bonded Si atoms. The change in symmetry between microcline and orthoclase results in a shift of about 0.23 eV.
Substitution of K+ by Na+ results in a further shift to higher binding
energies by 0.36 eV. In the plagioclase series increasing the coupled substitution of Ca2+ and Al3+ for Na+ and Si4+ results in a
decrease in the Si 2p core electron binding energy from
102.92 eV for albite to 102.45 eV for anorthite. A similar type of
shift has been observed in EPM analysis of the Si Ka [12].
Al 2p core-level spectra
Fig. 4 shows the Al 2p spectra obtained for the feldspars in comparison to that of corundum, a-Al2O3. The Al atoms in all feldspars
are tetrahedrally coordinated to four oxygen atoms and form SiO
Al linkages. Similar to the Si 2p core level spectra the Al 2p core
level spectra show a single Gaussian peak within a small range of
binding energies between 74.38 and 74.60 eV. The change in symmetry between microcline and orthoclase results in a shift of about
0.12 eV. Substitution of K+ by Na+ results in a further shift to higher
binding energies by 0.10 eV. In the plagioclase series increasing the
coupled substitution of Ca2+ and Al3+ for Na+ and Si4+ results in a
decrease in the Al 2p core electron binding energy from 74.62 eV
for albite to 74.35 eV for anorthite. A similar type of shift has been
observed in EPM analysis of the Al Ka [12]. In general a chemical
shift is caused by changes in the electrostatic potential eld experienced by the core electrons. The shift for the Al 2p core level
peaks is much less pronounced than for the Si 2p core level spectra
due to the aluminum avoidance rule, which indicates that each Al
tetrahedron will be surrounded by Si tetrahedral and visa versa
[13]. Therefore, even though the amount of tetrahedral Al increases
from albite to anorthite and since they are all surrounded by Si tetrahedral in the plagioclase crystal structure, the effect on the Al 2p
core level binding energies will be limited. Since the Al atomic
arrangement in a-Al2O3 is characterized by octahedral coordination instead of tetrahedral coordination a direct comparison with
the Al 2p spectra of the feldspars is impossible. It is well known,
and this study conrms this, that it is very difcult to unambiguously determine any chemical shifts in the Al 2p binding energies
among the feldspars, as these shifts are generally in the order of

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J.T. Kloprogge, B.J. Wood / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 711716

Fig. 2. XPS survey scans of the feldspars microcline, orthoclase and the plagioclase series albiteanorthite.

Table 1
Chemical compositions (at.%) based on XPS results after exclusion of the O 1s results.
Sample

Microcline

Orthoclase

Albite

Oligoclase

Andesine

Labradorite

Anorthite

Si
Al
K
Ca
Na

60.2
19.7
18.1
0.6
1.3

59.3
19.8
18.6
0.6
1.7

58.2
21.8
0.5
1.8
17.6

54.7
25.2
1.0
5.3
13.8

50.1
29.6
1.1
9.6
9.2

46.9
33.1

13.1
6.9

40.6
39.5

18.8
1.2

Microcline K0.905Na0.065Ca0.03AlSi3O8.
Orthoclase K0.890Na0.081Ca0.029Al1.010Si2.990O8.
Albite Na0.881Ca0.091K0.027Al1.090Si2.910O8.
Oligoclase Na0.686Ca0.264K0.050Al1.261Si2.739O8.
Andesine Na0.462Ca0.482K0.055Al1.486Si2.514O8.
Labradorite Na0.350Ca0.650Al1.655Si2.345O8.
Anorthite Na0.059Ca0.941Al1.972Si2.027O8.

Fig. 3. Si 2p high resolution spectra obtained for feldspars, in comparison with Si 2p of quartz, a-SiO2.

0.20.3 eV, which is not much more than the typical precision of
the XPS instrument [1417].
O 1s core-level spectra
A set of O 1s spectra obtained from the feldspars is shown in
Fig. 5. The overall shapes of the O 1s peaks observed for all specimens are similar. The chemical bonding of the O atoms with Al and
Si in the feldspars is complex. For the interpretation rst of all the

Al/(Al + Si) ratio for the tetrahedral sites is of importance, because

the AlO distances are about 0.13 larger than the SiO distances.
But, in addition, the SiO distance will be about 0.03 larger when
the oxygen atom is bonded to another Si than if it is bonded to Al.
The coordination of the oxygen atom to 0, 1, or 2 K, Na, or Ca atoms
has a further effect on the TO bond distances and the TOT
angles [18]. Since the charge density difference for each oxygen
atom may not vary signicantly, it is not expect to be able to
resolve all these binding energy differences. The bonding

J.T. Kloprogge, B.J. Wood / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 711716
Table 2
Binding energy (in eV), for Si(2p), Al(2p), and O(1s) orbitals observed for the feldspars.
Sample

Si 2p

Al 2p

O 1s

Microcline
Orthoclase
Albite
Oligoclase
Andesine
Labrodorite
Anorthite

102.79
102.56
102.92
102.71
102.67
102.68
102.45

74.38
74.50
74.62
74.52
74.46
74.39
74.35

531.89
531.92
531.96
531.69
531.63
531.58
531.48

715

same amount of Si, Al and K or Na bonding to the oxygen atoms

in its crystal structure. The spectra do show a small but visible
increase in binding energy from microcline to albite of about
0.07 eV, which is smaller than the typical precision of the XPS
instrument [1417]. In the plagioclase series increasing the coupled substitution of Ca2+ and Al3+ for Na+ and Si4+ results in a
decrease in the O 1s core electron binding energy from 531.96 eV
for albite to 531.48 eV for anorthite. This increase is slightly above
the typical precision of the XPS instrument and is therefore
thought to be real. In the albite unit cell there are 4 AlO4 tetrahedra, 12 SiO4 tetrahedra and 4 irregular Na sites, which changes to
6 AlO4 tetrehedra, 6 SiO4 tetrahedra and 4 irregular Ca sites in
anorthite. Therefore an increase in the number of AlOSi linkages
in the plagioclase structure results in a decrease in binding energy,
which is consistent with observations for Al2O3 and SiO2, where
the O 1s binding energy is also signicantly lower for the AlO
bond compared to the SiO bond [19]. The effect of the Ca2+ substituting for Na+ on the AlOSi and SiOSi linkages is very limited.
Valence-level spectra

Fig. 4. Al 2p high resolution spectra of the feldspars in comparison with the Al 2p of

corundum, Al2O3.

differences in the various O atoms in the feldspars can be analyzed

in terms of the total charge each receives from the surrounding
cations. Based on this one would expect the O 1s spectra to be
identical for microcline, orthoclase and albite, which all have the

Valence-level X-ray photoemission spectra are useful to characterize the nature of the chemical bonding, and may be directly
compared with the electron density of state (DOS) calculations.
The majority of the valence states are composed of oxygen 2s
and 2p atomic orbitals with overlap from Si and A1 3s and 3p
atomic orbitals [20].
Electronic structures of quartz (a-SiO2) and corundum (aAl2O3) have been thoroughly investigated both experimentally
and theoretically [for a-Al2O3, see e.g. [21,22], and for a-SiO2, e.g.
[23,24]]. In quartz, Si atoms are tetrahedral coordinated, whereas
Al atoms in corundum are all octahedral coordinated.
The lower-VB spectra observed from the four polymorphs are
shown in Fig. 6. The lower-VB spectra for microcline and orthoclase
are similar and appear intermediate between a-SiO2 and a-Al2O3
in terms of binding energies. In the plagioclase series increasing
coupled substitution of Na and Si for Ca and Al results in a change
of the overall shape of the spectra, showing a distinct broadening
associated with the presence of two separate but overlapping
bands. The binding energies of the two bands are similar to the
21 eV band observed for quartz and the 23 eV band observed for
corundum. Compared with O 1s peaks, the lower VB peaks are considerably broader (34 eV Full Width at Half Maximum, FWHM),
and therefore, detailed structures cannot be resolved. Thus, the differences in bonding are reected in the peak locations and their
shapes. Nevertheless, this implies that the bonding character for
microcline and orthoclase is more covalent than that of a-Al2O3,

Fig. 5. O 1s high resolution spectra of feldspars.

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J.T. Kloprogge, B.J. Wood / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 137 (2015) 711716

Fig. 6. Comparison of the lower valence band spectra of the feldspars with a-SiO2 and a-Al2O3.

but less than that of a-SiO2. In contrast, the plagioclase samples

show two distinct bonding characters that are comparable with
those of a-SiO2 and a-Al2O3.
For both a-SiO2 and a-Al2O3, the upper-VB consists of mainly
two features; a peak located at around 6 eV, and a peak at around
1112 eV [25]. Based on the DOS calculations, the features at 6 eV,
are predominantly O(p)-non-bonding states with little contribution from O(s). These non-bonding states are spatially localized
on the atomic sites and oriented transversally with respect to the
SiO and AlO bonding direction for the quartz and corundum
structures, respectively. The features at higher at 1112 eV mainly
consist of strongly hybridized orbitals. The calculations indicate
that these two features are well separated in both quartz and
corundum, reecting two distinct features found in calculated
DOS [25,26]. The upper valence bands for the feldspars are rather
featureless, suggesting that the orbital overlaps are much more
spread out over the energy range.
Conclusions
High resolution XPS has shown that the environment for Si
atoms in all feldspars is rather similar but different from quartz
due to the presence of second nearest neighbor Al. The difference
in symmetry between microcline and orthoclase is reected by a
shift of about .023 eV for Si 2p and about 0.12 for Al 2p. In the plagioclase series the coupled substitution of Ca2+ + Al3+ for Na+ + Si4+
results in a decrease of the Si 2p signal from 102.92 eV for albite to
102.45 eV for anorthite and similarly for the Al 2p signal from
74.62 eV to 74.35 eV, respectively. The shift in the Al 2p is much
less pronounced as a result of the aluminum avoidance rule, which
indicates that each Al tetrahedron will be surrounded by Si tetrahedral and visa versa. For the O 1s an increase in the number of
AlOSi linkages in the plagioclase structure results in a decrease
in binding energy from 531.96 eV for albite to 531.48 eV for anorthite, which is consistent with observations for Al2O3 and SiO2.
The lower-VB spectra for microcline and orthoclase are similar
and intermediate between a-SiO2 and a-Al2O3 in terms of binding
energies. In the plagioclase series increasing the coupled substitution results in a change of the overall shape of the spectra, showing
a distinct broadening associated with the presence of two separate
but overlapping bands similar to the 21 eV band observed for
quartz and the 23 eV band observed for corundum. The bonding
character for microcline and orthoclase is more covalent than that
of a-Al2O3, but less than that of a-SiO2. In contrast, the plagioclase
samples show two distinct bonding characters that are comparable
with those of a-SiO2 and a-Al2O3.

Acknowledgements
The authors wish to thank the Science and Engineering Faculty,
QUT for providing the feldspar samples used in this study. The
authors acknowledge the facilities, and the scientic and technical
assistance, of the Australian Microscopy & Microanalysis Research
Facility at the Centre for Microscopy and Microanalysis, The University of Queensland. The authors thank Bob Downs and Tom
Laestch of the Rruff project for the use of the XtlDraw software.
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