Originally published 22 November 2012; corrected 7 December 2012

www.sciencemag.org/cgi/content/full/science.1229450/DC1





Supplementary Materials for

Phase Transformations and Metallization of Magnesium Oxide at
High Pressure and Temperature
R. Stewart McWilliams,* Dylan K. Spaulding, Jon H. Eggert, Peter M. Celliers,
Damien G. Hicks, Raymond F. Smith, Gilbert W. Collins, Raymond Jeanloz
*To whom correspondence should be addressed. E-mail: stewartmcwilliams@gmail.com

Published 22 November 2012 on Science Express
DOI: 10.1126/science.1229450



This PDF file includes:

Materials and Methods
Figs. S1 to S6
Tables S1 to S3
References


Correction: References were corrected.
1

Materials and Methods
Materials and Targets
A laser target is shown in Figure 1A. Multi-layer targets for temperature and
reflectivity measurements consisted of a 50 m thick Al buffer with a 300 m thick
single crystal of MgO attached, stacked to produce a uniform-thickness sandwich ~ 1 mm
in diameter. The synthetic MgO, supplied by Marketech International, was oriented for
shock propagation in the <100> crystallographic direction. The initial density and index
of refraction (at 532 nm) were taken to be 3.584 g/cm
3
and 1.743, respectively (38). A
broadband anti-reflection coating centered at 532 nm was deposited on the free-surface.
Samples were kept in dry or vacuum conditions as much as possible to prevent water
adsorption. The Al buffer was diamond-turned to mirror finish, and coated on the
ablation surface with ~10 m of CH polymer.
The P-V measurements were referenced to a quartz standard (35, 39), so used a 30
m thick c-cut quartz (-SiO
2
) crystal inserted between the MgO and the Al buffer (34),
taken to have an initial density and index of refraction (532 nm) of 2.65 g/cm
3
and 1.546,
respectively (40).
Parts were bonded using Norland-63 optical adhesive with a glue thickness of less
than ~5 m for Al-sample bonds and less than ~1 m for SiO
2
-MgO bonds. Preheating
effects are negligible in these types of targets for the drive laser parameters used (41).
Drive Lasers
Experiments were conducted using the Omega (Laboratory for Laser Energetics,
University of Rochester) and Jupiter (Lawrence Livermore National Laboratory) laser
facilities (12, 13, 42). At the Omega Laser Facility, the laser drive consisted of six beams
2

of the Omega laser, smoothed by SG8 phase plates to provide an 800-m diameter spot
of uniform irradiation on target to ensure planar loading. Laser energies of 850 J in a 1
ns pulse were used. At the Jupiter Laser Facility, the drive laser consisted of two beams
of the Janus laser; CPP phase plates provided uniform irradiation of a 600-m diameter
spot; laser energies up to 500 J in a 2 ns pulse were used.
One-dimensional loading is evidenced in our data by lateral uniformity in shock
features over ~ 500 m on the target (Figs 1B, 1C).
VISAR
A line-imaging laser interferometer, or line VISAR (Velocity Interferometer
System for Any Reflector), measured the velocity and reflectivity of shock fronts in MgO
and quartz as functions of time and position in the target (42). A representative dataset is
shown in Fig. 1B. The shock velocity is
| |
(

+
+ =
0
) 1 ( 2
) ( ) ( ) (
n
t b t t U
S



(Eq. S1)
where t is the time, (t) is the observed fringe phase (a fraction of the fringe period, such
that a full period is unity), and b(t) is the integer number of base fringe shifts. The right
term is referred to as the VPF (velocity-per-fringe) in which is the wavelength of the
VISAR probe laser (532 nm), is the optical delay time introduced by the etalon placed
in one leg of the interferometer, (1+) is a correction for optical dispersion in the etalon,
and n
0
is the ambient index of refraction in the material where the reflecting shock is
propagating. For Fig. 1B, a VPF of 1.5673 km/s is used. Two independent VISAR
systems having different VPF were used in each shot to constrain b(t) unambiguously.
Background fringes in the VISAR from immobile reflecting surfaces in the optical path
3

(ghost fringes) were subtracted from our signal fringes with Fourier analysis (43), e.g.
between e
1
and e
6
in Fig. 1B.
Shock reflectivity, the coefficient of reflection between the shocked (opaque,
reflecting) and unshocked (transparent, ambient) states, was determined as
0
0
) (
) (
I
t I
R t R =
(Eq. S2)
where I(t) is the fringe intensity, corrected for probe beam power variation with time, and
I
0
is the initial fringe intensity due to reflection from a reference surface of known
reflectivity R
0
(in this case, diamond-turned aluminum against an adhesive layer, with R
0

~ 88%, which is observed early in the VISAR records). Fringe intensity was determined
from the fringe amplitude, measured via Fourier transform by filtering intensity
contributions from background (long wavelength) signals. At the Omega facility, the
probe power variation was measured in a reference image of the target obtained before
shocking it. While the intensity vs. time profile of the probe was constant, its timing
could shift slightly between images, so reference intensity was time-shifted when
normalizing the data; the accuracy of this shift was tested, for example, by ensuring
fringe intensity prior to shock breakout (i.e. before event e
1
in Fig. 1) was constant after
normalization. At the Jupiter facility, a portion of the probe beam was diverted before
reaching the sample and focused at the edge of the streak camera image to provide a
time-resolved intensity reference simultaneously with the experiment.
Hugoniot Compressibility Measurements
Our P-V-E-U
S
-U
P
Hugoniot measurements for MgO at P ~ 0.6 TPa (Figs 2D, S1,
S6, and Table S1) were accomplished in the manner of Ref. (34) using the quartz
Hugoniot (35, 39) and a thermodynamic description of the quartz reshock Hugoniot (34).
4

This technique consists of driving a reflecting shock through a standard material (quartz)
into the sample material (MgO). Measurement of shock velocity in each material at the
moment the shock transits the standard-sample interface allows a determination of the
shock Hugoniot by impedance matching.
Temperature Measurements
A Streaked Optical Pyrometer (SOP)

(44, 45) was used to measure thermal
emission from the shock front as a function of time and space, integrated over a 350 to
900 nm spectral window. A representative SOP dataset is shown in Figure 1C. In our
analysis, we apply a calibration based on the known shock temperatures in quartz (12).
To do this, experiments on quartz alone were conducted in parallel to the MgO
experiments to correlate emission intensity with a standard temperature (14). In these
calibration experiments, as in the MgO experiments, U
S
(t) and the spectral radiance L(t)
are simultaneously measured. Assuming grey-body behavior, L(t) is given by Plancks
Law as
| | 1 ) ( / exp
1 2
) ( ) (
5
2

=
t kT hc
hc
t t L

(Eq. S3)
where the emissivity (t) is given by Kirchhoffs Law assuming an optically thick shock
front
) ( 1 ) ( t R t = (Eq. S4)
Comparison of quartz measurements with the standard (12) gives a relationship between
the observed SOP intensity I
SOP
(t) and the temperature, defined as (44, 45)
|
|
.
|

\
|
+ =
) (
) (
1 ln
) (
0
t I
A t
t T
T
SOP

(Eq. S5)
5

where T
0
and A are fit parameters (Fig. S5) which are independent of material and
constant for all experiments provided the optical configuration of the pyrometer is
unchanged.
Calibration to a standard material (14), rather than a standard lamp of known
spectral radiance

(44, 45), provides several advantages, including the ability to fit Eq. S5
to a range of temperatures (rather than to a single point) and to temperatures which are
characteristic of the experiment (as opposed to the low temperature of a lamp), as shown
in Fig. S5. Straightforward corrections to temperature are possible with future
improvements to the standard.
Equation-of-State Modeling
A linear U
S
-U
P
model of compressibility on the Hugoniot provided a good
representation of the P-V-E-U
S
-U
P
data (Figs 2D and S1). This was defined by a
weighted linear fit, obtained by orthogonal distance regression, to appropriate MgO
Hugoniot data, giving U
S
= (6.743 0.070) + (1.316 0.017) U
P
. The y-intercept of this
fit agrees well with the bulk sound speed of MgO, 6.73 0.01 (32), showing the
reliability of the measurements and the fit. Data below U
S
= 9.3 km/s were excluded
because the shock exhibits two-wave structure in this regime (46) which can lead to
nonlinear U
S
-U
P
behavior. Also excluded was a datum obtained using the free-surface
release assumption U
f
= 2U
P
which clearly deviates from other Hugoniot data (47). It is
noted that the data of Marsh (30) used in this fit appears to be identical to the earlier data
reported by van Thiel (48) but shifted, possibly from changes in a standard Hugoniot; it is
presumed the later dataset was accurate, and the earlier dataset was omitted. For our high
pressure data, the quartz Hugoniot of Ref. (35) was assumed (Table S1).
6

Our multi-phase equation-of-state (EOS) for MgO is based on finite-strain and
Mie-Grneisen-Debye equations-of-state (16, 18). Basic thermodynamic differentials
(49)
PdV TdS dE = (Eq. S6)
dT C dV
V
C T
P dE
V
V
+ |
.
|

\
|
+ =

(Eq. S7)
dT
V
C
dV
V
K
dP
V T

+ = (Eq. S8)
dT
T
C
dV
V
C
dS
V V
+ =

(Eq. S9)
are used, where S is entropy, the Grneisen parameter, and K
T
the isothermal
compressibility. For shock states in a given pure phase and at thermodynamic
equilibrium, Hugoniot pressure P
H
can be defined as (16, 18)
2 / ) )( / ( 1
) ) ( )( / ( ) (
) (
0 H H
tr H S H H S
H H
V V V
E V E V V P
V P

+
=

(Eq. S10)
where the subscript H refers to conditions on the Hugoniot of the given phase, centered at
the initial P, T and V (P
0
, T
0
, V
0
, respectively, where V
0
is the ambient volume of the
initial phase), the subscript S refers to conditions on the isentrope of the given phase
(centered at P
0
, T
0
, and V
0
HP
, the ambient volume of the given phase), corresponds to
the given phase and is assumed to depend only on volume, and the energy of
transformation E
tr
is a difference in internal energy between the given phase and the
initial phase (E
tr
0 if the given phase is the initial phase). The Rankine-Hugoniot
relations (15, 49) give
| |
2 / 1
0 0 0
) /( ) (
H H S
V V P P V U = (Eq. S11)
7

| |
2 / 1
0 0
) )( (
H H P
V V P P U = (Eq. S12)
2 / ) )( (
0 0 H H H
V V P P E + = (Eq. S13)
The isentrope is defined by a third order Birch-Murnaghan equation (18)
(

+ + = f K f f K f P
S S S
) 4 (
2
3
1 ) 2 1 ( 3 ) (
/
0
2 / 5
0

(Eq. S14)
where f = (1/2)[(V
0
HP
/V)
2/3
-1], and K
0S
and K
0S
/
are the ambient bulk modulus and its first
pressure derivative, respectively, for isentropic conditions. From Eqs. S6-S9

= dV P V E
S S
) ( (Eq. S15)

= dV
V
T
V T
S

) ( (Eq. S16)
and

+
+ =
) (
) (
) ( ) (
H H
tr H S
V E
E V E V
H S H H
C
dE
V T V T
(Eq. S17)
The Debye model is used to determine S and C
V
(16)
)] 1 ln( ) ( ) 3 / 4 [( 6
3
x
gas
e x D R S

= (Eq. S18)
)] 1 /( 3 ) ( 4 [ 6
3
=
x
gas V
e x x D R C
(Eq. S19)
where

=
x
z
e
dz z
x
x D
0
3
3
3
1
3
) ( (Eq. S20)
and x = /T, where is the Debye temperature. This model gives C
V
6R
gas
in the high-
temperature regime observed in our experiments, consistent with our specific heat results
(Fig. 2).
8

It is assumed that /V = constant, and correspondingly that = V d d ln / ln

(16) in a given phase. We assume K
T
at given volume is temperature independent and
estimate it as (49)
|
|
.
|

\
|

+ |
.
|

\
|

|
.
|

\
|

=
H
H V H
H
H
H
T
V
T C P P
V
P
V
V V
K

2 2
) (
0 0
(Eq. S21)
(where C
V
corresponds to conditions on the Hugoniot) or, where the Hugoniot is
undefined (possible for high-pressure phases at large volume), as (50)
1
2
2
1

|
|
.
|

\
|
+
+ =
T K V C
T K V
K K
T V
S
S T

(Eq. S22)
(where K
S
, T, and C
V
correspond to the isentrope, and the thermal expansivity
V K C
T V
/ = ). Consistent with the assumption that K
T
(V) is temperature independent,
these two estimates are virtually identical for MgO at V where both can be calculated.
To summarize, within a given phase , and K
T
are functions of V alone; C
V

depends on V and T. Off-Hugoniot states in a given phase are determined using Eqs. S7-
S9. A phase is thus defined by 6 parameters: V
0
HP
(ambient volume, equal to V
0
for initial
phase), K
0S
and K
0S
/
(ambient elastic constants),
0
and
0,
(ambient thermodynamic
constants), and E
tr
(energy difference between phases).
Phase boundaries are located in P-T space where the Gibbs free energies of the
two relevant phases equalize; comparing the equations-of-state along the boundary yield
the entropies and volumes of transformation (S
tr
and V
tr
, respectively). To model the
phase transformation regimes, the Hugoniot was assumed to fall on the phase boundary in
P-T space (i.e. the transformation was modeled as if it occurred at equilibrium (15)), and
a linear U
S
-U
P
EOS was assumed for these regions. Model parameters (18 total) were
9

adjusted to match the data, with emphasis on fitting regions of the Hugoniot
corresponding to pure phases, and on locating phase boundaries at the observed
conditions of transformation. Phase transition properties (Table I) were established by
examining a variety of models that fit the data. Two example models are shown in Fig.
S6 with associated parameters given in Table S3. The ranges given for phase transition
properties (Table I) include the possibility that our T-U
S
data in transformation regimes is
representative of thermodynamic equilibrium (e.g. best-fit model) and the possibility
that it does not represent thermodynamic equilibrium, either due to nonequilibrium
transformation effects such as superheating or due to time-resolution limitations (e.g.
relaxed model).
Since transformation parameters and high-pressure phase equations-of-state are
determined relative to the B1 phase, it was important that the B1 phase model was as
accurate as possible (Table S3). We found it to be satisfactorily described by parameters
appropriate for B1 MgO determined near ambient conditions (19): density
0
= 3.584
g/cm
3
, bulk modulus and its pressure derivative K
0S
= 163.2 ( 0.7) GPa and K
0S
= 4.13
( 0.02), and Grneisen parameter
0
= 1.52 (0.02). We take
0
for the B1 phase to be
760 K. For our complete multi-phase models, we used somewhat different K
0S
and K
0S

(K
0S
= 162, K
0S
= 4.3) to enhance model agreement with the highest-pressure gas-gun
data (31, 33) (Figs S1, S6), presumed to also be in the B1-phase.
Details on Compilation of Table I
The results in Table I were compiled as follows. First, we characterized the
observed phase transformations using the equation-of-state modeling described above.
This established experimental ranges for the five quantities in Table I describing the
10

phase transformations (T, P, ( )
B
T P / , S
tr
, and V
tr
). The ranges of T and P
encompass the beginning and end of the transformations on the Hugoniot, and include
some model-dependant uncertainty; the ranges for the three other quantities represent
model-dependant uncertainties assessed by examining different parameters for the high
pressure phases. There are tradeoffs in selecting parameters for the high-pressure phases
that fit the measurements; for example, a large volume decrease at the first transition
must be accompanied by a relatively large volume increase at the second, to ensure good
agreement with compressibility data at higher pressure. The quantities S
tr
, T, and P are
found to be insensitive to the model parameters selected: that is, they are well constrained
by our data. The quantities V
tr
and ( )
B
T P / are poorly constrained, as indicated by
the larger fractional uncertainty of these quantities in Table I; this is due in part to the
lack of compressibility data in the first high pressure phase, such that the volume of this
phase is poorly constrained.
Second, we examined the properties of theoretical phase transformations that
most closely matched our observed phase transformations, for comparison to our
measurements. The P, T and ( )
B
T P /

of the theoretical transformations were taken
from the regions of the theoretical phase boundaries that were closest to the observed
transitions. Since predicted V
tr
and S
tr
on calculated phase boundaries were not
available in the literature, we estimated these quantities using various assumptions. For
the first transition, two limiting assumptions were examined. In one, V
tr
/V was
presumed constant on the phase boundary (and defined by the zero-temperature value
predicted in first-principles calculations), which gives an approximate upper bound for
V
tr
and S
tr
at high temperature. In the other, S
tr
was presumed constant on the phase
11

boundary and presumed to be infinitesimal (as it must be at low temperature), which sets
a lower bound of S
tr
~ V
tr
~ 0 at high temperature (since the Clapeyron slope, also
infinitesimal at low temperature, becomes finite at high temperature, requiring V
tr

become small). For the second transition, we assume that volume of transformation on
melting is roughly constant at high pressure, regardless of local phase.
Specific Heat Calculation
The specific heat analysis used here has been described previously (Refs (12, 13)
and references therein). From Eq. S7
( )
( ) T V V T
P V E
C
H
H
V
) / ( /
/
+
+
=
(Eq. S23)
For the results in Fig. 2B, was taken from first-principles calculations for pure solid and
liquid MgO at relevant conditions ( 1.1) (3). In using a corresponding to a pure
phase in this calculation, the C
V
measured are accurate where the Hugoniot accesses a
pure-phase state; this is likely the case where the measurements approach the Dulong-
Petit limit. In regions of the Hugoniot corresponding to phase transformation, C
V
should
deviate from the Dulong-Petit limit (as observed), however here C
V
is not accurate
because in a mixed-phase regime can differ from that in a pure phase. Put another way,
the apparent specific heat in these regimes is a combination of specific heat and latent
heat.
Decay Prediction
Below 0.5-0.6 TPa, reflection from the shock front could not be measured (R <
0.2%). Shock velocity in this regime was estimated by extrapolation from higher
pressure in a given experiment, using a double-exponential model fit to the visible decay
12

data, as in U
S
(t)=c
B
+A
1
exp(-t/
1
)+A
2
exp(-t/
2
), where c
B
is the bulk sound speed and A
1
,
A
2
,
1
,
2
are fit parameters. The form of this function was developed considering that U
S

tends to decay exponentially with time in decaying shocks (42) toward the bulk sound
speed (neglecting strength); a double rather than single exponential was selected to
improve fit agreement with the visible decay data.
Decaying shocks typically do not show significant changes in the velocity decay
rate due to phase transformations, and thus this extrapolation should be reasonable
through the first phase transformation. This can be seen in the data for the second
transformation in MgO (Fig. 1D), where clear shifts in the emission decay rate
(signifying the presence of a phase transformation) are not accompanied by any
detectable change in the observed velocity decay (as verified by fitting across the region
in question with the exponential decay function). Similarly, simple exponential, or
nearly-exponential decay behavior is observed through the melting transitions of diamond
(13) and quartz (12) and in a wide range of other cases where underlying material
transformations occur.
We conclude that this extrapolation is accurate for MgO since 1) integrated travel
distances

dt t Us ) ( across the MgO (i.e. from e

1
to e
6
in Fig. 1D) including the
extrapolated velocities agree with sample thicknesses, and 2) the data produced with this
extrapolation are in good agreement with known Hugoniot temperatures in the B1 phase
(3, 36) and specific heats in the extrapolated regime are consistent with the Dulong-Petit
limit except during the first temperature anomaly. For example, if the extrapolation were
offset from the true velocity by 1 km/s below the first transition, Hugoniot temperatures
measured at low pressure would deviate noticeably from those in the B1 phase (the
13

measured temperatures would shift in pressure by ~60 GPa at low pressure). We estimate
based on this criterion that systematic errors on the order of ~0.5 km/s in the extrapolated
velocities are possible, but these do not substantially alter our conclusions or
measurements.
Also, this extrapolation and our analyses assume a single shock at all times in our
experiments, even through phase transformations; this is justified below.
Single-Shock Stability
Substantial volume decrease at phase transitions on the Hugoniot can lead to the
formation of multiple shocks, which would be inconsistent with our single-shock
analysis. A single shock is stable if (49)
1
2 1
1 0
0 1
1 2
>

V V
V V
P P
P P

(Eq. S24)
where subscript 1 indicates conditions at the peak Hugoniot state in the low-pressure
phase, and subscript 2 indicates a state on the Hugoniot above this (i.e. within the
subsequent phase transition regime). Geometrically, this criterion can be evaluated by
examining the Hugoniot in P-V space (Fig. S6). Given the possible large increase in
density at the first transition, we considered whether this could lead to formation of a
two-wave structure. However, all EOS models tested are consistent with the occurrence
of only a single shock. For example, in an extreme model (with large volume decrease at
the first transition, Fig. S6), the left side of Eq. S24 is ~ 2; and it is larger for other
models.
Drude-Semiconductor Conductivity Model:
Shock front reflectivities beyond a few percent in insulating materials suggest the
presence of delocalized electrons and enhanced electronic conductivity (12-14, 43). The
14

model used here to invert R, T, and V in shock-compressed MgO for electronic
conductivity is similar to that used in numerous prior studies (Refs (12, 43) and
references therein). For wide band-gap insulators, the quantitative results of this model
have been broadly supported by independent theory, e.g. for SiO
2
(12) and LiF (43).
Reflectivity is analyzed in terms of the Fresnel equation for normal incidence, R =
|(n-n
0
)/(n+n
0
)|
2
, where n = [
b
+4i()/]
1/2
is the complex index of refraction,
b
is the
contribution of the bound electrons, is the frequency, and () is the conductivity,
assumed to follow the Drude formulation () = (2n
e
e
2
/m
eff
)(1-i)
-1
, where n
e
is the
carrier density, is the carrier relaxation time, and m
eff
is the carrier effective mass. It is
assumed that scattering occurs at the Ioffe-Regel limit (51), such that
e
v / = where v
e
is
the carrier velocity and
3 / 1
) 4 / 3 ( 2
F A
N N MV =

is the interatomic distance, where M is
molar mass, N
A
is Avogadros number, and N
F
is the number of atoms in a formula unit.
Carrier activation is assumed to follow the behavior of an intrinsic semiconductor (52),
i.e. )] 2 /( [ ) 2 / ( 2
2 / 1
2 / 3 2
kT E f kT m n
g eff e
= , where dy e y x f
x y m
m
) 1 /( / 2 ] [
0

+ =
is the Fermi-Dirac integral and E
g
is the activation gap energy. Carrier velocity is given
by )]) 2 /( [ / )] 2 /( [ )( / 2 (
2 / 1 2 / 3
kT E f kT E f m kT v
g g eff e
= . This model has three
independent variables based on observation (V, R and T) and three unknown parameters
(
b
, E
g
and m
eff
) which in this study are fit to the measurements.
The unknown parameters were further parameterized for optimum fitting in the
presence of distinct phase transitions. We assume a volume-dependent energy gap (E
g
)
between valence and conduction bands (12, 43), assumed to be sigmoidal in form as
15

(

+ =

T
T g
E E E exp
0

(Eq. S25)
where the density = 1/V, and E
0
, E
T
,
T
, and are fit parameters. This allows for rapid
changes in the gap at phase transitions or for more continuous change across a broader
pressure range. In the latter limit, Eq. S25 is similar to the linear function of density
commonly used for materials that lack a sharp phase transition (e.g. refs (12, 43) and
references therein). In one present fit, the parameter E
0
was fixed at 8 eV, the ambient-
pressure gap of the B1 phase, and the predicted gap of the B2 phase (1); this choice was
made considering that the reflectivity at low pressure can be attributed solely to bound
electron effects (Figs S2 and S3) and therefore cannot meaningfully constrain the initial
gap. A second fit with an unconstrained initial gap gave broadly similar conclusions
regarding gap closure at the second transition (Fig. 2C and Fig. S4).
The quantity
b
was fit either as a constant, or such that the quantity
b
(equal
to the real index of refraction at low conductivity) was a linear function of density.
Constrained by the low-pressure end of the reflectivity data, where the reflectivity is
attributable to bound electron effects alone (Fig. S2),
b
gives an independent estimate for
the real index of refraction of MgO under pressure (Fig. S3). This model-based
measurement of the real index agrees reasonably well with extrapolation of shock data
from lower pressures (17).
Optical Depth of Shocked MgO
A small optical depth in shocked MgO is required in the present experiments for
accurate interpretation of the temperature data, such that emission originates from near
shock-front, and hence Hugoniot states, rather than from well behind the shock, where
16

material undergoing rarefaction may lie off the Hugoniot or where target interfaces can
contribute anomalously to the emission. That is, we require that shocked MgO have an
optical thickness on the order of or less than the distance U
S
t where t is the time
resolution of the diagnostics (~100 ps), or ~1 m.
Several lines of evidence support a small optical depth in shocked MgO at the
conditions of our experiments:
1) The DC electronic conductivity is expected to be ~ 1000 S/m or larger in these
experiments, based on the Drude-semiconductor model results (Fig. S4), and also on
predicted carrier densities for warm solid MgO

(1). Estimating the optical penetration
depth d at a conducting surface (here, the shock front) as 8 / ~ c d

(strong conductor)
and k c d 2 / =

(arbitrary material) (53), where k is the imaginary part of the index and
can be estimated from our model, we estimate a maximum d of ~ 0.3 m and ~ 2 m,
respectively, in our experiments.
2) It is observed that above T ~ 8000 K and P ~ 0.3 TPa the data show good consistency
with prior measurements (36) and predictions (3, 36) of shock temperature, and as
discussed adhere closely to the Dulong-Petit limit. These observations would be highly
unlikely if the temperature data were in error. Below T ~ 8000 K, however, the apparent
temperature deviates from previously reported temperatures, suggestive of a large optical
skin depth at low T and P. This is not unexpected given that nearly-critical d are inferred
for the solid at conditions near the first transition. These observations evince the
accuracy of our temperature measurements except at low pressures (P < 0.3 TPa) where
the data were discarded.
17

3) We note that shocked MgO was opaque to VISAR in all experiments accessing the
present pressure range (including experiments with peak pressures at P < 0.3 TPa); this is
consistent with our conclusion of strongly absorbing conditions in solid MgO at high
temperature, though other sources of opacity (i.e. scattering) could contribute.
Data Quality and Measurement Uncertainties
Data collected at the Omega laser are considered to be of substantially higher
quality than those collected at the Jupiter laser (as discussed below), and T-U
S
-R data
from Omega have thus been used in our quantitative analyses here; lower-accuracy and
lower-precision measurements of T-U
S
-R from the Janus laser have been included to
demonstrate that primary observations the existence of a temperature minimum on the
Hugoniot (Table S2), and the onset of shock reflectivity (Fig. S2) can be reproduced in
very different experimental configurations.
Error in the temperature (Fig. 2A error bars) is primarily systematic, such that
derivatives of temperature, e.g. ( )
H
V T / , and quantities calculated from derivatives,
e.g. C
V
, are known more precisely. A comparison between Omega and Jupiter results for
the first transition temperature are presented in Table SII. Random error in temperature
is small, as is evident in the high reproducibility of measurements at a given facility (Figs
2A and 2B, and Table SII). Temperatures at the Omega laser are considered more
accurate due to improved diagnostic quality and improved accuracy in the relative timing
of VISAR and SOP datasets. Error in reflectivity at Omega (Fig. 2C and Fig. S2 error
bars) is also mostly systematic; the reproducibility of the measurements confirms that
random errors are small except at very high pressure. At Jupiter (Fig. S2 error bars)
reflectivity uncertainty is much larger and principally random in nature.
18

Compressibility data were collected at the Jupiter laser. Uncertainty in these
results (Table S1) is considered random, consistent with the observed scatter in the
datapoints; additional systematic sources of error due to the choice of reference EOS
have been discussed (Figs S1 and S6), and are not included in Table S1.
All uncertainties reported here are equivalent to one standard deviation.

19


Fig. S1:
Linear U
S
-U
P
fit to available shock data, as discussed in Supplementary Materials and
Methods, plotted with a theoretical U
S
-U
P
EOS (3) and two EOS models from this study
(see Fig. S6). Present measurements are shown using the standard quartz Hugoniots from
Ref. (39) (HEA) and Ref. (35) (KD); the latter was used in the linear fit.
20


Fig. S2:
Shock reflectivity R vs. shock velocity U
S
. Grey and black curves are separate shots from
Omega; blue curve is a compilation of reflectivities from four Jupiter shots. At both
facilities, reflectivity became observable above U
S
=17.3 km/s, though the data from
Omega are more precise. The green curve shows the predicted reflectivity based on
extrapolation of the real index of refraction from shock data to P=0.023 TPa (U
S
=7.8
km/s) (17), which agrees well with the lowest reflectivities observed here. This suggests,
independent of our Drude-semiconductor model analysis, that the reflectivity observed
below the second transition is principally due to bound electron contributions, and that
the rise beginning at ~18 km/s can be attributed to an increase in conductivity associated
with the second transformation.
21


Fig. S3:
Real component of the index of refraction of MgO at low conductivity. Green and blue
solid lines are given by
b
in the present Drude-semiconductor model fits (for assumed
constant
b
or
b
varying linearly in density, respectively) with dashed portions
representing extrapolations beyond the reflectivity data. Solid black line is from Ref.
(17), with dashed line indicating extrapolation to high density.
22



Fig. S4:
DC conductivities (=0) and carrier densities inferred from the Drude-semiconductor
model, showing results for a constrained (E
0
=8 eV) and unconstrained (E
0
fit) initial gap.
The predicted carrier density on a 10,000 K isotherm in solid (B2) MgO

(1) is consistent
with our model results; this isotherm overlaps the Hugoniot at 0.49 TPa (here, predicted
carrier densities are ~10
19
cm
-3
while observed carrier densities are 10
19
to 10
20
cm
-3

depending on model assumptions).

23


Fig. S5:
Pyrometer temperature-intensity relationship determined from measurements on a
decaying shock in quartz (red). The data is fit (dashed black line) to obtain T
0
and A in
Eq. S5. Note that the pyrometer is calibrated at temperatures corresponding to the phase
transitions in MgO.
24


Fig. S6:
Mie-Grneisen-Debye, finite-strain EOS models for MgO; two example models are
presented with prior gas gun data (30-33, 36) and present measurements of T vs. U
S
(2
shots, colored as in Fig. 2), and P vs. V (2 shots). The best fit model required that
Hugoniot temperature data is precisely fit in mixed-phase regimes, whereas the relaxed
model examined the possibility of small density changes at transformation and deviations
from the data in mixed-phase regimes. Systematic uncertainty due to the reference EOS
of quartz (HEA (39), KD (35)) is of the same order of magnitude as random error, and
was accounted for. Also shown is the Hugoniot model of Ref. (3) which overlaps our
model exactly in the B1 phase, and is similar to the relaxed model for the first phase
transformation.

25

Table S1.
Hugoniot compressibility measurements from two experiments. Quartz Hugoniot of Ref.
(35) used.


Shot Laser
facility
MgO U
S

(km/s)
MgO U
P

(km/s)
MgO P
(TPa)
MgO
(g/cm
3
)
Quartz U
S

(km/s)
MgO6 Jupiter 18.82 (0.49) 9.48 (0.42) 0.639 (0.030) 7.22 (0.40) 18.41 (0.46)
MgO7 Jupiter 18.88 (0.49) 8.96 (0.40) 0.606 (0.028) 6.82 (0.34) 17.98 (0.45)


26


Table S2.
Temperature of the first transition as measured at the Jupiter and Omega laser facilities.
The temperature minimum at the high-pressure end of the coexistence regime (U
S
16.5
km/s) was selected as a reference point.


Shot Laser
facility
Temperature minimum (K)
(at P ~ 0.44 TPa)
MgO16 Jupiter 9540 (+850,-620)
MgO17 Jupiter 9522 (+850,-620)
MgO19 Jupiter 9068 (+850,-620)
MgO29 Jupiter 9930 (+850,-620)
MgO31 Jupiter 9881 (+850,-620)
57513 Omega 8610 (+790, -752)
57514 Omega 8432 (+790, -752)
Jupiter Average 9588 (+850,-620)
Omega Average 8521 (+790, -752)



27


Table S3.
Equation-of-state parameters for the two example models shown in Figs S1 and S6.

Best-fit model Relaxed model
B1 Phase
V
0
(cc/g) 0.2790
K
0S
(GPa) 162
K
0S
/
(unitless) 4.3

0
(unitless) 1.5

0
(K) 760
E
tr
(J) 0
First High Pressure Phase
V
0
HP
/ V
0-B1
0.862 0.927
K
0S
/ K
0S-B1
1.3 1.2
K
0S
/
/K
0S-B1
/
1.1 1.1

0
/
0-B1
1 1

0
/
0-B1
0.52 0.58
E
tr
/ (V
0-B1
K
0S-B1
) 0.3 0.175
Second High Pressure Phase
V
0
HP
/ V
0-B1
0.92 0.972
K
0S
/ K
0S-B1
1.2 1.2
K
0S
/
/K
0S-B1
/
1.18 1

0
/
0-B1
1 1

0
/
0-B1
0.415 0.44
E
tr
/ (V
0-B1
K
0S-B1
) 0.25 0.225

28

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