Interplay of computer simulations and x-ray absorption spectra in the study of the bromide hydration structure
Abstract
X-ray absorption spectra (EXAFS and XANES) were generated from snapshots of a Monte Carlo (MC) simulation of a bromide ion aqueous solution and from model structures. The MC simulation relies on a recently developed and tested polarizable potential based on ab initio potential energy surfaces. A comparison with the experimental K-edge Br spectrum of a 0.3 M YBr3 aqueous solution was performed. XANES spectra are reproduced acceptably only if statistical fluctuations are included, which is performed in this work by using snapshots from computer simulation. As expected, single scattering BrO contributions are dominant in the case of the EXAFS region. Due to this fact, Br- in water is a good model system for studying the influence of the distribution of distances on the determination of structural parameters. Then, a parallel study of the data analysis procedure of the experimental EXAFS spectrum and those theoretically computed from the structures supplied by the MC simulation, was carried out. The shape of the distribution function and its asymmetry must be taken into account in a practical way to obtain a more accurate determination of the BrO first-shell distance. A further refinement consists in using the computer simulation to extrapolate the BrO distance from the experimental EXAFS spectrum. In this way, a BrO distance of 3.44±0.07 Å and a coordination number of 6±0.5 were determined
Full text
I
n
e
p
lay
o
c
o
m
pu
e
si
m
u
la
i
on
s a
nd
x
-
ay a
b
s
o
p
i
on
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p
ec
a
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e s
ud
y
o h
e
b
o
m
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h
y
d
a
i
on
s
u
c
u
e
P
a
ick J
.
M
e
kli
ng,
R
eg
l
a
A
y
a
l
a,
J
o
s
e
´M
.
M
a
ı
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ne
z
,
R
a ae
l R
.
P
appa
l
a
do,
and
E
n
i
que
S
a
´
n
c
he
z M
a
c
o
s
a
)
Depa
amen
o de Qu
ı
´m
i
ca F
ı
´
s
i
ca, Un
i
e
s
i
dad de Se
ill
a, 41012-Se
ill
a, Spa
i
n
R
ece
i
ed 4 Ap
il
2003
;
accep
ed 1
J
u
l
y 2003
X- ay ab
s
o p
i
on
s
pec
a EXA
FS
and XANE
S
we e gene a
ed o
m s
nap
s
ho
s
o a
M
on
e
C
a
l
o
M
C
s
i
m
u
l
a
i
on o a b o
m
i
de
i
on aqueou
s s
o
l
u
i
on and o
m m
ode
l
s
uc
u e
s
. The
M
C
s
i
m
u
l
a
i
on
e
li
e
s
on a ecen
l
y de e
l
oped and
e
s
ed po
l
a
i
zab
l
e po
en
i
a
l
ba
s
ed on ab
i
n
i i
opo
en
i
a
l
ene gy
s
u ace
s
. A co
m
pa
i
s
on w
i
h
he expe
i
m
en
a
l
K
-edge
B
s
pec
u
m
o a 0.3
M
Y
B
3aqueou
s
s
o
l
u
i
on wa
s
pe o
m
ed. XANE
S
s
pec
a a e ep oduced accep
ab
l
y on
l
y
i
s
a
i
s
i
ca
l fl
uc
ua
i
on
s
a e
i
nc
l
uded, wh
i
ch
i
s
pe o
m
ed
i
n
h
i
s
wo k by u
s
i
ng
s
nap
s
ho
s
o
m
co
m
pu
e
s
i
m
u
l
a
i
on. A
s
expec
ed,
s
i
ng
l
e
s
ca
e
i
ng
B
O con
i
bu
i
on
s
a e do
m
i
nan
i
n
he ca
s
e o
he EXA
FS
eg
i
on. Due
o
h
i
s
ac
,
B
i
n wa
e
i
s
a good
m
ode
l
s
y
s
e
m
o
s
udy
i
ng
he
i
n
fl
uence o
he d
i
s
i
bu
i
on o
d
i
s
ance
s
on
he de
e
m
i
na
i
on o
s
uc
u a
l
pa a
m
e
e
s
. Then, a pa a
ll
e
l
s
udy o
he da
a ana
l
y
s
i
s
p ocedu e o
he expe
i
m
en
a
l
EXA
FS
s
pec
u
m
and
ho
s
e
heo e
i
ca
ll
y co
m
pu
ed o
m
he
s
uc
u e
s s
upp
li
ed by
he
M
C
s
i
m
u
l
a
i
on, wa
s
ca
i
ed ou
. The
s
hape o
he d
i
s
i
bu
i
on unc
i
on
and
i
s
a
s
y
mm
e
y
m
u
s
be
aken
i
n
o accoun
i
n a p ac
i
ca
l
way
o ob
a
i
n a
m
o e accu a
e
de
e
m
i
na
i
on o
he
B
O
fi
s
-
s
he
ll
d
i
s
ance. A u
he e
fi
ne
m
en
con
s
i
s
s
i
n u
s
i
ng
he co
m
pu
e
s
i
m
u
l
a
i
on
o ex
apo
l
a
e
he
B
O d
i
s
ance o
m
he expe
i
m
en
a
l
EXA
FS
s
pec
u
m
. In
h
i
s
way, a
B
O d
i
s
ance o 3.44 0.07 Å and a coo d
i
na
i
on nu
m
be o 6 0.5 we e de
e
m
i
ned. © 2003
Ame
i
can In
s
i
u
e o
Phy
s
i
c
s
.DOI
:
10.1063
/
1.1603719
I. I
NTR
O
DUCT
I
O
N
The
s
uc
u e o
i
on
i
c
s
o
l
u
i
on
s
ha
s
been a
m
a
e o
i
nc ea
s
i
ng
i
n
e e
s
o
m
expe
i
m
en
a
l
and
heo e
i
ca
l
po
i
n
s
o
i
ew.1–3 The
m
a
i
n expe
i
m
en
a
l
echn
i
que
s
o
s
uc
u a
l
s
ud
i
e
s
o
s
uch
s
y
s
e
ms
a e x- ay d
i
ac
i
on X
R
D , neu
on
d
i
ac
i
on ND , and x- ay ab
s
o p
i
on
s
pec
o
s
copy XA
S
.
A
l
hough X
R
D and ND can y
i
e
l
d
s
uc
u a
l i
n o
m
a
i
on
abou
d
i
s
o de ed
s
y
s
e
ms
li
ke
m
o
s
li
qu
i
d
s
,
he
i
accu acy
dec ea
s
e
s s
ong
l
y
i
n
he ca
s
e o
m
u
l i
co
m
ponen
s
y
s
e
ms
X
R
D o equ
i
e
s
con
s
i
de ab
l
e
s
yn
he
i
c e o
s
o pe o
m
he
i
s
o
op
i
c
s
ub
s
i
u
i
on
s
ND .4,5 Th
i
s
ac
e
s
i
c
s
he
i
u
s
e,
a
s
doe
s
he need o e
l
a
i
e
l
y h
i
gh concen
a
i
on
s
.
Si
nce
he
1980
s
, one o
he XA
S
echn
i
que
s
, ex
ended x- ay ab
s
o p-
i
on
fi
ne
s
uc
u e EXA
FS
, ha
s
been app
li
ed
o de
e
m
i
ne
he p
s
eudopa
i
a
l
pa
i
co e
l
a
i
on unc
i
on
s
o a
o
ms
i
n bo
h
c y
s
a
lli
ne and a
m
o phou
s s
y
s
e
ms
.6
B
ecau
s
e XA
S i
s
e
l
e
m
en
-
s
pec
ifi
c,
he
l
oca
l
s
uc
u e a ound one
ype o a
o
m
can be ob
a
i
ned by EXA
FS
. Add
i i
ona
ll
y,
i
can be app
li
ed
o
a
l
a ge ange o concen
a
i
on
s
, ang
i
ng
yp
i
ca
ll
y o
m
a ew
m
illi
m
o
l
a
o
s
e e a
l
m
o
l
a .
X- ay ab
s
o p
i
on
s
pec
o
s
copy ha
s
ad
i i
ona
ll
y been
s
ubd
i
i
ded, acco d
i
ng
o
wo ene gy eg
i
on
s
o a
s
pec
u
m
:
x- ay ab
s
o p
i
on nea -edge
s
uc
u e XANE
S
, wh
i
ch co e-
s
pond
s
o
he nea -edge eg
i
on
ha
ex
end
s
o
m
he
h e
s
h-
o
l
d
o abou
50 eV abo e
he edge, and EXA
FS
, wh
i
ch ex-
end
s
o
m
ene g
i
e
s
o abou
50
o
m
o e
han 1000 eV abo e
he edge.
Si
nce
he k
i
ne
i
c ene gy o
he pho
oe
l
ec
on
i
s
l
ow
i
n
he XANE
S
eg
i
on,
m
u
l i
p
l
e
s
ca
e
i
ng
M
S
e ec
s
a e
do
m
i
nan
,
ha
i
n
he pa
i
cu
l
a ca
s
e o
i
on
i
c
s
o
l
u
i
on
s
a e
m
o
s
l
y due
o
s
ca
e
i
ng pa
hway
s
be
ween a
o
ms
o
he
fi
s
and
s
econd
s
o
l
a
i
on
s
he
ll
s
a ound
he ab
s
o be a
o
m
. In
he
XANE
S
eg
i
on, bo
h geo
m
e
i
ca
l
and e
l
ec
on
i
c de
a
il
s
a -
ec
he
s
hape o a
s
pec
u
m
, and
he e o e
he e
i
s
no gen-
e a
l
, d
i
ec
, e
l
a
i
on
s
h
i
p be
ween
s
pec
u
m
and geo
m
e
y a
s
i
n
he ca
s
e o EXA
FS
.7Th
i
s
i
s
why
he
echn
i
que
i
s
o
en
u
s
ed a
s
a
fi
nge p
i
n
o cha ac
e
i
z
i
ng
he ne
i
ghbo hood o
he ab
s
o be a
o
m
.8
In
he EXA
FS
eg
i
on,
he
s
ca
e ed pho
oe
l
ec
on ha
s
a
h
i
gh k
i
ne
i
c ene gy,
s
o
ha
s
i
ng
l
e back
s
ca
e
i
ng p oce
ss
e
s
a e do
m
i
nan
. Howe e ,
m
u
l i
p
l
e
s
ca
e
i
ng pheno
m
ena
m
ay
con
i
bu
e no
i
ceab
l
y
o
he
s
pec
u
m
,
m
ak
i
ng
i
s
i
n
e p e
a-
i
on
m
o e d
i
fi
cu
l
. In o de
o ex
ac
i
n o
m
a
i
on con
a
i
ned
i
n an EXA
FS
s
pec
u
m
, a nu
m
be o
s
i
m
p
li
y
i
ng a
ss
u
m
p-
i
on
s
ha e
o be
m
ade.
B
ea
i
ng
i
n
m
i
nd
ha
he nu
m
be and
co e
l
a
i
on o a
i
ab
l
e
s
needed
i
n
he EXA
FS
ana
l
y
s
i
s
i
s
o
en
s
upe
i
o
o
he
i
n o
m
a
i
on con
a
i
ned
i
n
he EXA
FS
s
pec
u
m
,7,9–11
he u
s
e o
i
n o
m
a
i
on de
i
ed o
m
o
he
s
ou ce
s
,
li
ke co
m
pu
a
i
ona
l
m
e
hod
s
,
i
s
o
s
pec
i
a
l i
n
e e
s
.
Th
i
s
p ocedu e ha
s
p o en
o be
s
ucce
ss
u
l i
n
m
any
s
ud
i
e
s
o
s
uc
u a
l
e
l
uc
i
da
i
on o
s
o
li
d and
li
qu
i
d
s
y
s
e
ms
.12–17
The a
i
m
o
h
i
s
wo k
i
s
o ob
a
i
n
he b o
m
i
de hyd a
i
on
s
uc
u e by
m
ean
s
o
he co
m
b
i
na
i
on o expe
i
m
en
a
l i
n o -
m
a
i
on de
i
ed o
m
XA
S
echn
i
que
s
and
heo e
i
ca
l
da
a
o
m
co
m
pu
e
s
i
m
u
l
a
i
on
s
. When dea
li
ng w
i
h
he
s
uc
u a
l
de
s
c
i
p
i
on o
i
on
i
c
s
o
l
u
i
on
s
,
he pa
e n
s
o
he ca
i
on and
an
i
on hyd a
i
on a e a o
m s
i
m
il
a ,
m
o
s
l
y due
o
wo ea-
s
on
s
.
Fi
s
o a
ll
, an
i
on en
i
on
m
en
i
s m
a
i
n
l
y de
e
m
i
ned by
he e
s
u
l
an
o ce o
he co
m
pe
i i
on be
ween
i
on–d
i
po
l
e
i
n-
aE
l
ec
on
i
c
m
a
il:
s
anchez@
s
i
m
u
l
ux.u
s
.e
s
J
OU
R
NAL O
F
C
HE
M
I
C
AL
P
HY
S
I
C
S
VOLU
M
E 119, NU
M
B
E
R
13 1 O
C
TO
B
E
R
2003
66470021
-
9606/2003/119
(
13
)
/6647/8/$20.00
©
2003
A
m
e
ic
an In
s
i
u e o
P
h
ysics
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
e ac
i
on
s
, wh
i
ch
end
o a o
s
y
mm
e
i
c hyd ogen a
o
ms
a ange
m
en
s
a ound
he an
i
on-oxygen ax
i
s
, and hyd ogen
bond
i
ng
o
he an
i
on, wh
i
ch a o
s
an a
s
y
mm
e
i
c a ange-
m
en
o
i
s s
u ound
i
ng wa
e
m
o
l
ecu
l
e
s
o
m
ax
i
m
i
ze
he
hyd ogen bond
i
n
e ac
i
on. The
s
econd ea
s
on
i
s
ha
he
e
l
ec
on den
s
i
y d
i
s
i
bu
i
on
i
s m
o e expanded a ound
he
nuc
l
eu
s
i
n
he an
i
on ca
s
e wha
e
s
u
l
s
i
n
m
o e
i
m
po
an
fi
s
- and
s
econd-o de pe
u ba
i
on
s
w
i
h e
s
pec
o
he
l
oca
l
e
l
ec
i
c
fi
e
l
d
s
. The
s
e
wo ea
s
on
s
an
i
c
i
pa
e no
i
ceab
l
e d
i
e -
ence
s
i
n
he
s
o
l
en
o gan
i
za
i
on a ound ca
i
on
s
and an
i
on
s
,
i
n pa
i
cu
l
a o
m
onoa
o
m
i
c o
s
i
m
p
l
e
i
on
s
. In add
i i
on,
he
weak b o
m
i
de–wa
e
i
n
e ac
i
on
s
i
m
p
l
y ex
e
m
e
l
y a
s
s
o
l
en
-exchange a
e
s
o
he
fi
s
s
o
l
a
i
on
s
he
ll
. A
ll
he
s
e
ea
s
on
s m
ake
he XA
S
s
udy o
he b o
m
i
de hyd a
i
on qu
i
e
d
i
e en
o
m
he
s
udy o h
i
gh
l
y cha ged ca
i
on
s
p e
i
ou
s
l
y
ca
i
ed ou
by ou g oup.18–25 Ob
i
ou
s
l
y,
he
s
en
s
i i
i
y o
he EXA
FS
echn
i
que
o
he d
i
s
o de
m
ake
s
he
s
uc
u a
l
ana
l
y
s
i
s
o
h
i
s s
y
s
e
m m
o e d
i
fi
cu
l
. Thu
s
,
he u
s
e o
heo-
e
i
ca
l i
n o
m
a
i
on
i
s
expec
ed
o
s
hed
li
gh
on
i
.
S
e e a
l
au
ho
s
ha e p e
i
ou
s
l
y exa
m
i
ned
he b o
m
i
de
hyd a
i
on w
i
h
he he
l
p o
heo e
i
ca
l
oo
l
s
. Wa
ll
en e
a
l
.26
u
s
ed
m
o
l
ecu
l
a dyna
m
i
c
s s
i
m
u
l
a
i
on
s
o gene a
e
heo e
i
ca
l
EXA
FS
s
pec
a w
i
h
he p og a
m
F
E
FF
and
he e o
l
u
i
on a
s
a
unc
i
on o p e
ss
u e and
e
m
pe a
u e o EXA
FS
and XANE
S
s
pec
a wa
s
ana
l
yzed. D’Ange
l
oe
a
l
.27
s
ud
i
ed a
l
s
o EXA
FS
s
pec
a w
i
h
he p og a
m
GNXA
S
, and co
m
b
i
ned
M
D
s
i
m
u
l
a-
i
on e
s
u
l
s
w
i
h a
s
ho
ange
m
ode
l
d
i
s
i
bu
i
on ba
s
ed on
Ga
mm
a unc
i
on
s
o
fi
he EXA
FS
s
pec
u
m
. Howe e ,
none o
he
m
ca
l
cu
l
a
ed
he b o
m
i
de XANE
S
s
pec
u
m
.
One o
he
m
o
s
co
mm
on a
ss
u
m
p
i
on
s m
ade
o ca
l
cu
l
a
e
XA
S
s
pec
a
i
s
o educe
he
s
y
s
e
m
o a
s
i
ng
l
e
s
uc
u e.
Ne e
he
l
e
ss
,
he con
i
bu
i
on o
m m
o
l
ecu
l
e
s
and a ange-
m
en
s
i
n
s
an
aneou
s
l
y d
i
s
o
ed ha
s
an
i
m
po
an
e ec
on
he a e age
s
pec
u
m
,22,25 e
s
pec
i
a
ll
y
i
n
l
ab
il
e
s
uc
u e
s
li
ke
he b o
m
i
de
i
on hyd a
i
on. In
h
i
s s
en
s
e,
he po
ss
i
b
ili
y o
con
s
i
de
i
ng
s
a
i
s
i
ca
l i
n o
m
a
i
on
m
ake
s
he ana
l
y
s
i
s
p oce-
du e ea
s
i
e . A ecen
l
y de e
l
oped b o
m
i
de–wa
e
i
n
e ac
i
on
po
en
i
a
l
, wh
i
ch
i
nc
l
uded
he po
l
a
i
zab
ili
y o pa
i
c
l
e
s
ba
s
ed
on ab
i
n
i i
oda
a and who
s
e good beha
i
o ha
s
ecen
l
y been
checked by co
m
pu
e
s
i
m
u
l
a
i
on
s
,28 w
ill
be e
m
p
l
oyed
i
n
h
i
s
co
m
b
i
ned expe
i
m
en
a
l
–
heo e
i
ca
l
s
udy. I
i
s
wo
h po
i
n
-
i
ng ou
ha
he
heo e
i
ca
l
s
pec
a a e co
m
pu
ed o
m
fi
s
p
i
nc
i
p
l
e
s
,
s
i
nce no e
m
p
i
i
ca
l
pa a
m
e
e
s
we e
i
n
oduced
ne
i
he
i
n
he
i
n
e
m
o
l
ecu
l
a po
en
i
a
l
s
, no
i
n
he co
m
pu
a-
i
on o
he XA
S
s
pec
a. The XANE
S
s
pec
u
m
w
ill
be co
m
-
pu
ed o
m
a ep e
s
en
a
i
e
s
e
o geo
m
e
i
e
s
ex
ac
ed o
m
he
s
a
i
s
i
ca
l
a
j
ec
o y. W
i
h e
s
pec
o
he EXA
FS
ana
l
y
s
i
s
,
on one
s
i
de
he
M
D po
en
i
a
l
s
ha
ll
be p obed, on
he o
he
s
i
de, de
a
il
s
o
he
s
uc
u a
l
de
e
m
i
na
i
on w
ill
be
i
n e
s
i
-
ga
ed.
II.
M
E
TH
O
D
O
L
OG
Y
Theo e
i
ca
l
XANE
S
and EXA
FS
s
pec
a o
he
B
K
-edge 13 474 eV a e ca
l
cu
l
a
ed by a co
m
b
i
na
i
on o
s
a-
i
s
i
ca
l
and quan
u
m
-
m
echan
i
ca
l
ca
l
cu
l
a
i
on
s
. The
s
udy o
he b o
m
i
de hyd a
i
on wa
s
pe o
m
ed u
s
i
ng
h ee ap-
p oache
s
: i
co
m
pu
a
i
on o XANE
S
s
uc
u e
s
o
m
quan
u
m
-
m
echan
i
ca
ll
y
m
i
n
i
m
i
zed c
l
u
s
e
s
w
i
hnwa
e
m
o
l
-
ecu
l
e
s
(4 n7)
; ii
co
m
pu
a
i
on o XANE
S
s
pec
a
ak-
i
ng
i
n
o accoun
he
s
a
i
s
i
c
s
h ough
M
on
e
C
a
l
o
s
i
m
u
l
a-
i
on
s
nap
s
ho
s
; iii
ana
l
y
s
i
s
o EXA
FS
s
pec
a
i
n
wo way
s
:
on
he one hand,
he expe
i
m
en
a
l
s
pec
u
m
wa
s
co
m
pa ed
o
a
heo e
i
ca
ll
y co
m
pu
ed one o
m
M
on
e
C
a
l
o
s
i
m
u
l
a
i
on
s
nap
s
ho
s
;
on
he o
he hand,
he
fi i
ng p ocedu e o
he
EXA
FS
s
pec
u
m
wa
s
ca
i
ed ou
on bo
h
s
pec
a,
he ex-
pe
i
m
en
a
l
one and
he one co
m
pu
ed o
m
M
on
e
C
a
l
o
s
i
m
u
l
a
i
on
s
. The co
m
pa
i
s
on o
he
fi
s
wa
s
ca
i
ed ou
w
i
h
he a
i
m
o
e
s
i
ng
he a
li
d
i
y o
he
m
ode
l
s
uc
u e
s
u
s
ed
o
de
s
c
i
be
he b o
m
i
de hyd a
i
on.
The expe
i
m
en
a
l
B
K
-edge XA
S
s
pec
a u
s
ed
i
n
h
i
s
wo k o 0.3
M
aqueou
s s
o
l
u
i
on
s
o Y
B
3we e
m
ea
s
u ed a
bea
m
li
ne
B
L12
C
o
he
P
ho
on
F
ac
o y
i
n T
s
ukuba,
J
apan.
The
i
ng cu en
wa
s
300
m
A, and
he
i
ng ene gy 2.5 GeV.
A h
i
gh e
s
o
l
u
i
on
Si
311 channe
l
-cu
m
onoch o
m
a
o wa
s
u
s
ed.
C
a
li
b a
i
on wa
s
ca
i
ed ou
w
i
h
he
L
2-edge o a Au
o
il
13734 eV . Da
a we e co
ll
ec
ed
i
n
an
sm
i
ss
i
on
m
ode
u
s
i
ng
i
on
i
za
i
on cha
m
be
s
a
s
de
ec
o
s
.
The quan
u
m
-
m
echan
i
ca
ll
y op
i
m
i
zed
s
uc
u e
s
u
s
ed o
ob
a
i
n
i
ng XANE
S
s
pec
a we e
aken o
m
a p e
i
ou
s s
udy
on
he
m
i
c o
s
o
l
a
i
on o
he b o
m
i
de
i
on
i
n wa
e ,
m
e
hano
l
,
and ace
on
i
il
e.29 In
h
i
s s
udy,
B
(H2O)nc
l
u
s
e
s
(1
n8) we e op
i
m
i
zed a
he
B
3LY
P l
e e
l
w
i
h doub
l
e-
ba
s
i
s s
e
s
aug
m
en
ed w
i
h po
l
a
i
za
i
on and d
i
u
s
e unc
i
on
s
.
S
a
i
s
i
ca
l i
n o
m
a
i
on wa
s
ob
a
i
ned o
m
M
on
e
C
a
l
o
M
C
s
i
m
u
l
a
i
on
s
u
s
i
ng
fi
s
-p
i
nc
i
p
l
e
s
b o
m
i
de–wa
e
i
n
e -
ac
i
on po
en
i
a
l
s
ecen
l
y de e
l
oped by ou g oup.28
F
o
h
i
s
po
en
i
a
l
,
he
M
ob
il
e
C
ha ge Den
s
i
y
i
n Ha
m
on
i
c O
s
c
ill
a-
o
s
M
ode
l
wa
s
e
m
p
l
oyed
o de
s
c
i
be b o
m
i
de an
i
on and
wa
e
s
pec
i
e
s
, bo
h o
he
m
be
i
ng po
l
a
i
zab
l
e, and
he wa
e
fl
ex
i
b
l
e. The wa
e –wa
e
i
n
e ac
i
on
s
we e de
s
c
i
bed by a
M
C
DHO po
en
i
a
l
p e
i
ou
s
l
y de
s
c
i
bed by
he
C
ue na aca
g oup,
M
ex
i
co.30 The e
li
ab
ili
y o
he e
s
u
l
s
de
i
ed o
m
nu
m
e
i
ca
l
s
i
m
u
l
a
i
on
s
depend
s
c
i i
ca
ll
y on
he po
en
i
a
l
m
ode
l
de
s
c
i
b
i
ng
he
i
n
e ac
i
on
s
a
m
ong
he
s
i
e
s
de
fi
n
i
ng
he
s
y
s
e
m
. The
i
n
e ac
i
on po
en
i
a
l
u
s
ed ha
s
a
l
eady been
e
s
ed
i
n p e
i
ou
s s
ud
i
e
s
,28 whe e
he
s
i
m
u
l
a
ed
s
y
s
e
ms
s
how a good ag ee
m
en
w
i
h expe
i
m
en
a
l
e
s
i
m
a
i
on
s
. The
M
C
s
i
m
u
l
a
i
on
s
we e ca
i
ed ou
w
i
h
he
M
C
HANG p og a
m
de e
l
oped by
he g oup o
C
ue na aca.31 The
s
y
s
e
m s
i
m
u-
l
a
ed con
s
i
s
s
o 1
B
211 wa
e
m
o
l
ecu
l
e
s
i
n
he NVT
en
s
e
m
b
l
e a
300 K u
s
i
ng
he
P
OT–2
i
n
e ac
i
on po
en
i
a
l
o
m
R
e . 28.
P
e
i
od
i
c bounda y cond
i i
on
s
we e app
li
ed,
and
l
ong- ange
i
n
e ac
i
on
s
we e co
m
pu
ed by
he Ewa
l
d
s
u
m m
e
hod,
i
nc
l
ud
i
ng a
e
m
o accoun
o
he ne
cha ge
o
he
s
y
s
e
m
.32,33
F
u
he de
a
il
s
abou
he
M
C
s
i
m
u
l
a
i
on
s
a e g
i
en
i
n
R
e . 28.
K
-Edge XANE
S
s
pec
a o
B
i
n wa
e we e ca
l
cu
l
a
ed
o
m
40
s
nap
s
ho
s
aken e e y 120 K (K 103) con
fi
gu a-
i
on
s
o a
M
C
s
i
m
u
l
a
i
on. The
s
i
m
u
l
a
ed XANE
S
s
pec
u
m
i
s
an a e age o e
he
s
pec
a o
he
s
nap
s
ho
s
. XA
S
s
pec
a
ha e been co
m
pu
ed w
i
h
he
F
E
FF
8.10 p og a
m
code34 de e
l
-
oped by
R
eh ’
s
g oup. The po
en
i
a
l
ca
l
cu
l
a
i
on
s
u
s
e
he
Hed
i
n–Lundq
i
s
s
e
l
-ene gy app ox
i
m
a
i
on.35 A
s
e
l
-
con
s
i
s
en
fi
e
l
d p ocedu e
S
C
F
wa
s
e
m
p
l
oyed. A 6.0 Å cu
-
o ad
i
u
s
wa
s
cho
s
en o
he
S
C
F
ea
m
en
and o
he
u
ll
-
m
u
l i
p
l
e
s
ca
e
i
ng pa
h
s
, en
s
u
i
ng
he
i
nc
l
u
s
i
on o
he
s
econd
s
o
l
a
i
on
s
he
ll i
n
he co
m
pu
a
i
on o
he
s
pec
a. A
m
u
fi
n-
i
n po
en
i
a
l
wa
s
app
li
ed w
i
h o e
l
ap c
i
e
i
a o 1.0
6648
J
.
C
he
m
.
P
h
ys
.,
V
o
l
. 119,
N
o. 13, 1
O
c
obe
2003
M
e
kli
ng
e a
l
.
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
ouch
i
ng
s
phe e
s
, 1.15 and 1.15 o
B
, O, and H a
o
ms
,
e
s
pec
i
e
l
y. The
s
e c
i
e
i
a we e de
e
m
i
ned ad hoc bu
cou
l
d
be
j
u
s
ifi
ed w
i
h
he
i
on
i
c na
u e o
he ab
s
o b
i
ng a
o
m
. I
wa
s
ound
ha
he
S
C
F
ad
i
u
s
cou
l
d be
l
owe ed
o 5.0 Å
w
i
hou
a ec
i
ng
he e
s
u
l
s
. A XANE
S
s
pec
u
m
ca
l
cu
l
a
ed
o
m
200
s
nap
s
ho
s
aken e e y 250 K con
fi
gu a
i
on
s
and
S
C
F
cu
o o 5.0 Å y
i
e
l
d
s
e y
s
i
m
il
a e
s
u
l
s
.
In p e
i
ou
s s
ud
i
e
s
on ca
i
on hyd a
i
on
s
uc
u e,12,22,24,25
he
i
nc
l
u
s
i
on o hyd ogen a
o
ms
p o ed
nece
ss
a y o ob
a
i
n
i
ng a ea
li
s
i
c back
s
ca
e
i
ng po
en
i
a
l
bu
l
ed
o a
s
en
s
i
b
l
e deg ada
i
on o
he
s
pec
u
m
when
hey
we e
i
nc
l
uded a
s
back
s
ca
e e
s
. D
i
fi
cu
l i
e
s
a e
m
a
i
n
l
y a
ss
o-
c
i
a
ed w
i
h an o e e
s
i
m
a
i
on o
he back
s
ca
e
i
ng con
i
bu-
i
on, bu
h
i
s
doe
s
no
a ec
he
i
o
l
e
i
n
he
s
e
l
-con
s
i
s
en
fi
e
l
d ca
l
cu
l
a
i
on o
he po
en
i
a
l
.16 In
he ca
s
e o b o
m
i
de
hyd a
i
on
s
uc
u e, ou e
s
u
l
s
u
s
i
ng
he
F
E
FF
p og a
m
i
nd
i
-
ca
ed
ha
he
s
i
m
u
l
a
ed
s
pec
a a e
m
o e
s
i
m
il
a
o
he ex-
pe
i
m
en
a
l
one
s
bo
h EXA
FS
and XANE
S
when hyd ogen
a
o
ms
a e
i
nc
l
uded a
s
back
s
ca
e e
s
. O
he au
ho
s
, who do
no
u
s
e
he
s
a
m
e
m
e
hodo
l
og
i
ca
l
app oach
o co
m
pu
e
he
EXA
FS
s
pec
a, wo k w
i
h
he a
ss
u
m
p
i
on o u
s
i
ng hyd o-
gen a
o
ms
a
s
back
s
ca
e e
s
i
n bo
h an
i
on and ca
i
on
s
ud
i
e
s
.17 The d
i
e en
s
a
egy hand
li
ng ca
i
on and an
i
on
hyd a
i
on, apa
o
m
i
s
heu
i
s
i
ca
l j
u
s
ifi
ca
i
on a
s s
een
i
n
Fi
g
s
. 3 and 4, cou
l
d be unde
s
ood by
he p e
s
ence o a
c
l
o
s
e
s
hyd ogen
s
he
ll
a ound
he an
i
on. The b o
m
i
de
i
on
i
nduce
s
he p e
s
ence o a
s
e
o hyd ogen a
o
ms
o
fi
s
-
s
he
ll
wa
e
m
o
l
ecu
l
e
s
i
n
i
s
c
l
o
s
e
s
i
c
i
n
i
y, wh
i
ch a e ound
o
p
l
ay a
s
i
gn
ifi
can
o
l
e
i
n bo
h
he pho
oe
l
ec
on
s
ca
e
i
ng
pheno
m
enon and
he de
e
m
i
na
i
on o e
l
ec
on
i
c wa e unc-
i
on
s
o
he b o
m
i
de c
l
u
s
e
s
.
A
s
i
m
p
lifi
ed exp e
ss
i
on o
he EXA
FS
unc
i
on
i
s
g
i
en
by6
k
j
N
j
kR
j
2S0
2k F
j
k e 2
j
2k2e2R
j
/
(k)
s
i
n 2kR
j
j
k, 1
whe e (k)
i
s
he
o
a
l
a
m
p
li
ude a
s
a unc
i
on o
he ec
o
kand
he
s
u
mm
a
i
on goe
s
o e a
ll
pa
h
s
j
.
N
j
i
s
he coo d
i
-
na
i
on nu
m
be , R
j
i
s
ha
l
o
he pa
h
l
eng
h, S0
2(k)
i
s
he
a
m
p
li
ude educ
i
on ac
o , F
j
(k)
i
s
he back
s
ca
e
i
ng a
m
-
p
li
ude,
j
2
i
s
he
s
econd-o de cu
m
u
l
an
known a
s
he
Debye–Wa
ll
e DW ac
o , (k)
he
m
ean ee pa
h o
he
pho
oe
l
ec
on, and
j
(k)
he pha
s
e-
s
h
i
.
In Eq. 1 ,
he d
i
s
o de
i
s
de
s
c
i
bed by
he DW ac
o .
None
he
l
e
ss
, when
heo e
i
ca
l i
n o
m
a
i
on de
i
ed o
m
nu-
m
e
i
ca
l
s
i
m
u
l
a
i
on
s
i
s
con
s
i
de ed,
s
uc
u a
l fl
uc
ua
i
on
s
a ound
he an
i
on a e
i
m
p
li
c
i
w
i
h
i
n
he
s
a
m
p
li
ng o
he con-
fi
gu a
i
ona
l
s
pace. Then,
he EXA
FS
unc
i
on can be a
l
e -
na
i
e
l
y exp e
ss
ed a
s
22
k1
N
s
i
s
uc
j
pa
h
s
N
j
kR
ij
2S0
2k F
j
k e 2R
i j
/
(k)
s
i
n 2kR
i j j
k, 2
whe e
N
s
i
s
he nu
m
be o
s
uc
u e
s
con
s
i
de ed
i
n
h
i
s
ca
s
e
10 000
s
uc
u e
s
e en
l
y
s
paced o e 50
M
(
M
106)
M
C
con
fi
gu a
i
on
s
,
i
goe
s
o e
he
s
uc
u e
s
de
i
ed o
m
he
s
a
i
s
i
ca
l
s
a
m
p
li
ng, and
j
o e
he pa
h
s
. The o
l
e p
l
ayed by
he exponen
i
a
l
con
a
i
n
i
ng
he DW ac
o o Eq. 1
i
s
e-
p
l
aced by an a e age o e
s
uc
u e
s
i
n Eq. 2 . In o de
o
check
he con e gence o
he e
s
u
l
s
, a co
m
pu
a
i
on w
i
h
40000
s
uc
u e
s
e en
l
y
s
paced o e 200
M
con
fi
gu a
i
on
s
wa
s
a
l
s
o pe o
m
ed. No d
i
e ence
s
we e ound be
ween
bo
h a e aged
s
pec
a.
F
u
he exa
m
p
l
e
s
o
h
i
s
a e ag
i
ng
o e
s
i
m
u
l
a
ed
s
pec
a
m
ay be ound
i
n
R
e
s
. 12, 15, 26, 36,
and 37.
The cu
-o ad
ii
s
e
l
ec
ed we e
he
s
a
m
e a
s
ho
s
e cho
s
en
i
n
he XANE
S
s
pec
a. The con
s
i
de ed pa
h
s
we e e
s
i
c
ed
o a
l
eng
h o up
o 7.0 Å and an a
m
p
li
ude o a
l
ea
s
9% o
he
i
n
en
s
i
y o
he
s
ho
e
s
B
H pa
h.
S
uc
u a
l
pa a
m
e
e
s
we e ob
a
i
ned o
m
bo
h expe
i
-
m
en
a
l
and
heo e
i
ca
l
s
pec
a by
m
ean
s
o
fi i
ng a
m
ode
l
s
uc
u e
o Eq. 1 .
C
on
ac
i
on pa
i
s
cou
l
d be exc
l
uded, a
s
appea ed a
s
we
ll
o
m
he ana
l
y
s
i
s
o
he Y
K
-edge.38 Thu
s
,
he
m
ode
l
s
uc
u e cho
s
en
i
s
he hexahyd a
ed c
l
u
s
e cde-
p
i
c
ed
i
n
Fi
g. 1. EXA
FS
da
a we e ana
l
yzed w
i
h
he
F
E
FF
IT
2.55
s
o
wa e package.39 The
fi i
ng o
he expe
i
m
en
a
l
EXA
FS
s
i
gna
l
o Eq. 1
i
s
ba
s
ed on a
s
anda d non
li
nea
l
ea
s
s
qua e
s
echn
i
que we
ll
-e
s
ab
li
s
hed
i
n
he
li
e a
u e.40
III.
R
ES
ULT
S
AND D
I
S
CU
SS
I
O
N
A
.
X
AN
ES
s
p
ec
a
C
a
l
cu
l
a
ed XANE
S
s
pec
a o
m
a
s
e
i
e
s
o quan
u
m
-
m
echan
i
ca
ll
y
m
i
n
i
m
i
zed
s
uc
u e
s
con
a
i
n
i
ng be
ween 4 and
7 wa
e
m
o
l
ecu
l
e
s
a e d
i
s
p
l
ayed
i
n
Fi
g. 2 a and co
m
pa ed
w
i
h
he expe
i
m
en
a
l
s
pec
u
m
. The geo
m
e
i
e
s
o
he
s
uc-
u e
s s
e
l
ec
ed a e
s
hown
i
n
Fi
g. 1. The ca
l
cu
l
a
ed XANE
S
s
pec
a
s
how no
i
ceab
l
e d
i
e ence
s
, e
s
pec
i
a
ll
y w
i
h e
s
pec
o
he e
l
a
i
e
i
n
en
s
i
y o
he e
s
onance
s
. To
he con
a y,
he ene gy a
l
ue
s
o
he
fi
s
wo e
s
onance
s
wh
i
ch appea a
13 472 and 13 489 eV, e
s
pec
i
e
l
y, a e ep oduced ea
s
on-
ab
l
y we
ll
by a
ll
o
he
m
and a e
i
n ag ee
m
en
w
i
h
he ex-
pe
i
m
en
a
l
s
pec
u
m
. The co
m
pa
i
s
on w
i
h
he expe
i
m
en
a
l
s
pec
u
m s
how
s
ha
he a
i
o o
he he
i
gh
s
o
he e
s
o-
nance
s
i
s
no
ep oduced. Wha
i
s m
o e,
he
m
a
i
n e
s
onance
o
he expe
i
m
en
a
l
s
pec
u
m
i
s
w
i
de and h
i
ghe
han
he
one
s
o
he co
m
pu
ed
s
pec
a.
XANE
S
s
pec
a a e gene a
ll
y con
s
i
de ed
o be
i
n
s
en
s
i
-
i
e
o d
i
s
o de , bu
cha ac
e
i
s
i
c o
he coo d
i
na
i
on geo
m
-
e
y. In
he ca
s
e o b o
m
i
de hyd a
i
on, whe e
he hyd a
i
on
s
uc
u e
i
s
no
we
ll
de
fi
ned,
he
s
en
s
i i
ene
ss
o
he XANE
S
s
pec
u
m
o
he
i
n
s
an
aneou
s
geo
m
e
i
e
s
can be
ill
u
s
a
ed
on
h ee
s
uc
u e
s
p
i
cked ou
o
he 40 con
s
i
de ed
o ca
l
cu-
F
IG. 1. Geo
m
e
i
e
s
o
he quan
u
m
-
m
echan
i
ca
ll
y op
i
m
i
zed
s
uc
u e
s
u
s
ed
o ca
l
cu
l
a
e XANE
S
s
pec
a o
Fi
g. 2 a .
6649
J
.
C
he
m
.
P
h
ys
.,
V
o
l
. 119,
N
o. 13, 1
O
c
obe
2003
B
o
mi
de h
y
d
a
i
on
s
u
c
u
e
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
l
a
e
he a e age
s
a
i
s
i
ca
l
s
pec
u
m
Fi
g. 2 b . On
he one
hand, and un
li
ke
he ca
s
e o
he quan
u
m
-
m
echan
i
ca
ll
y op
i
-
m
i
zed c
l
u
s
e
s
,
s
o
m
e o
he
i
nd
i
i
dua
l
s
pec
a exh
i
b
i
m
o e
i
n
en
s
e e
s
onance
s
han
he expe
i
m
en
a
l
one. On
he o
he
hand,
he
i
nd
i
i
dua
l
XANE
S
s
pec
a d
i
e
m
o e be
ween
each o
he ,
han
ho
s
e co
m
pu
ed o
m
quan
u
m
-
m
echan
i
ca
l
s
uc
u e
s
. Th
i
s s
en
s
i i
i
y o
he XANE
S
s
pec
a
o geo-
m
e
i
ca
l
change
s
o
m
he
fl
uc
ua
i
on
s
o
he
s
y
s
e
m s
up-
po
s s
ong
l
y
he need
o
i
nc
l
ude
s
a
i
s
i
ca
l i
n o
m
a
i
on
i
n
he
s
i
m
u
l
a
i
on o XANE
S
s
pec
a o b o
m
i
de
s
o
l
u
i
on
s
. I a
un
i
que
m
ode
l
s
uc
u e had been
aken
i
n
o con
s
i
de a
i
on,
he d
i
s
c epanc
i
e
s
be
ween
heo e
i
ca
l
and expe
i
m
en
a
l
s
pec-
a wou
l
d ha e been a
s
c
i
bed
o
he app ox
i
m
a
i
on
s
con
s
i
d-
e ed
i
n
he quan
u
m
co
m
pu
a
i
on
s
needed
o gene a
e
he
s
pec
u
m
, and e en
ua
ll
y,
he
s
e
m
i
e
m
p
i
i
ca
l
app ox
i
m
a
i
on
s
i
n
oduced
i
n ob
a
i
n
i
ng
s
o
m
e o
he pa a
m
e
e
s
. In
he
s
a
m
e
fi
gu e,
he co
m
pu
ed
s
pec
a u
s
i
ng
he
s
uc
u e
s
unca
ed
o
he
fi
s
s
o
l
a
i
on
s
he
ll
a e
s
hown. The
i
nd
i
i
dua
l
s
pec
a a e
s
ong
l
y a ec
ed by
he
unca
i
on, wha
ill
u
s
a
e
s
how
XANE
S i
s s
en
s
i i
e
o
he
s
o
l
a
i
on beyond
he
fi
s
s
he
ll
, a
s
a
l
eady ob
s
e ed
i
n
he ca
s
e o ca
i
on hyd a
i
on.24,25
In
Fi
g. 3,
he co
m
pa
i
s
on o
he a e aged ca
l
cu
l
a
ed
s
pec
u
m
o
m s
a
i
s
i
ca
l i
n o
m
a
i
on and
he expe
i
m
en
a
l
one
i
s s
hown.
B
o
h
he po
s
i i
on o
he
wo
m
a
i
n e
s
onance
s
and
he a
i
o o
he
i
he
i
gh
s
ag ee. A
s
expec
ed o
m
he
qua
li
a
i
e ana
l
y
s
i
s
o
he
m
e
hodo
l
ogy u
s
ed,
he w
i
d
h o
he
m
a
i
n e
s
onance o
he a e aged
s
a
i
s
i
ca
l
s
pec
u
m
i
s
m
o e
s
i
m
il
a
o
he expe
i
m
en
a
l
one
han
ha
ob
a
i
ned o
m
a un
i
que
s
uc
u e. Ne e
he
l
e
ss
,
he ac
ha
he
i
n
en
s
i
y o
he
m
a
i
n e
s
onance
i
nc ea
s
e
s
when a g ea
nu
m
be o
s
pec
a
de
i
ed o
m
d
i
e en
s
uc
u e
s
i
s
i
nc
l
uded,
i
s s
i
k
i
ng.
In o de
o
s
udy
he
s
en
s
i i
i
y o
he XANE
S
eg
i
on
o
he ab
s
o be -back
s
ca
e e d
i
s
ance,
he XANE
S
s
pec
u
m
ha
s
been eca
l
cu
l
a
ed con
s
i
de
i
ng
he
s
a
m
e po
i
n
s
o
he con-
fi
gu a
i
ona
l
s
pace, bu
i
nc
l
ud
i
ng on
l
y
s
o
l
en
m
o
l
ecu
l
e
s
o
he
fi
s
s
o
l
a
i
on
s
he
ll
. Acco d
i
ng
o
he ad
i
a
l
d
i
s
i
bu
i
on
unc
i
on o
he
M
C
s
i
m
u
l
a
i
on
s
,28 a
m
o
l
ecu
l
e be
l
ong
s
o
he
fi
s
s
o
l
a
i
on
s
he
ll
when
he
B
O d
i
s
ance
i
s
l
owe
han 4.1
Å. The a e aged
s
pec
u
m
ob
a
i
ned
i
s
i
nc
l
uded
i
n
Fi
g. 3
s
ho
da
s
hed
li
ne and d
i
e
s s
li
gh
l
y o
m
he one con
a
i
n-
i
ng
m
o e
han one hyd a
i
on
s
he
ll
da
s
hed
li
ne . Th
i
s
beha -
i
o
i
s
d
i
e en
o
m
he one ound by ou g oup
i
n
he
s
udy
o ca
i
on hyd a
i
on.22,24,25 In
he
l
a
e ca
s
e,
s
pec
a ca
l
cu-
l
a
ed o
m s
uc
u e
s
ha
con
a
i
ned on
l
y one
s
o
l
a
i
on
s
he
ll
p e
s
en
ed a
m
o e
i
n
en
s
e
m
ax
i
m
u
m
, and a
s
li
gh
d
i
s
p
l
ace-
m
en
and na ow
i
ng o
he
m
a
i
n e
s
onance wa
s
ob
s
e ed.
The e ec
o
he wa
e
m
o
l
ecu
l
e
s
beyond
he
fi
s
hyd a
i
on
s
he
ll
on
he a e aged XANE
S
s
pec
u
m
i
s sm
a
ll i
n
he ca
s
e
o
he b o
m
i
de hyd a
i
on, un
li
ke wha
i
s
ob
s
e ed when
co
m
pu
i
ng
he e ec
o h
i
ghe
s
he
ll
s
o
i
nd
i
i
dua
l
s
nap-
s
ho
s
. Thu
s
,
i
doe
s
no
s
ee
m
po
ss
i
b
l
e
o e
i
e e non
i
i
a
l
s
uc
u a
l i
n o
m
a
i
on beyond
he
fi
s
hyd a
i
on
s
he
ll
o
h
i
s
an
i
on
i
n
s
ud
i
e
s
o
s
o
l
u
i
on che
m
i
s
y. The ca
l
cu
l
a
ed
XANE
S
s
pec
u
m
u
s
i
ng a cu
o ad
i
u
s
o 6.0 Å, whe e hy-
d ogen a
o
ms
we e no
i
nc
l
uded a
s
back
s
ca
e e
s
,
i
s
a
l
s
o
p
l
o
ed
i
n
Fi
g. 3 do
ed
li
ne
s
. Th
i
s
co
m
pu
ed
s
pec
u
m
d
i
-
e
s s
i
gn
ifi
can
l
y o
m
he o
he
s
pec
a
i
nc
l
uded
i
n
he
fi
g-
u e.
B
.
EX
AF
S
s
p
ec
a
The co
m
pa
i
s
on o
he expe
i
m
en
a
l
and
heo e
i
ca
l
EXA
FS
s
pec
a
i
n
e
ms
o (k)k2
i
s
d
i
s
p
l
ayed
i
n
Fi
g. 4.
The ag ee
m
en
be
ween bo
h
s
pec
a
i
s s
a
i
s
ac
o y, e
s
pe-
c
i
a
ll
y con
s
i
de
i
ng
ha
no e
m
p
i
i
ca
l
pa a
m
e
e
s
we e
i
n-
c
l
uded
i
n
he co
m
pu
a
i
on o
he
heo e
i
ca
l
s
pec
u
m
. When
H a
o
ms
a e exc
l
uded a
s
back
s
ca
e e
s
,
he ag ee
m
en
i
s
ound
o be a o
m s
a
i
s
ac
o y,
s
uppo
i
ng
he
i
m
po
ance
o hyd ogen a
o
ms
i
n
he XA
S
s
pec
a o
he ha
li
de aqueou
s
s
o
l
u
i
on
s
.41–44 A
s
h
i
gh
li
gh
ed
i
n
he
s
e p e
i
ou
s
wo k
s
,
h
i
s
i
s
F
IG. 2. Expe
i
m
en
a
l
B
K
-edge XANE
S
s
o
li
d
li
ne and
he one
s
co
m
pu
ed
o
m
quan
u
m
-
m
echan
i
ca
ll
y op
i
m
i
zed
s
uc
u e
s s
hown
i
n
Fi
g. 1. b Ind
i
-
i
dua
l
XANE
S
s
pec
a co
m
pu
ed o d
i
e en
s
nap
s
ho
s
, e
i
he e
s
i
c
ed
o
fi
s
hyd a
i
on
s
he
ll
da
s
hed
li
ne
s
o no
s
o
li
d
li
ne
s
.
F
IG. 3. Expe
i
m
en
a
l
B
K
-Edge XANE
S
s
o
li
d
li
ne and co
m
pu
ed o
m
M
C
s
i
m
u
l
a
i
on
s
, e
i
he u
s
i
ng
fi
s
hyd a
i
on
s
he
ll
s
ho
da
s
hed
li
ne , o up
o 6 Å
l
ong da
s
hed
li
ne . The hypo
he
i
ca
l
ca
s
e whe e H a
o
ms
a e no
i
nc
l
uded a
s
back
s
ca
e e
s
i
s s
hown
i
n do
ed
li
ne
s
.
6650
J
.
C
he
m
.
P
h
ys
.,
V
o
l
. 119,
N
o. 13, 1
O
c
obe
2003
M
e
kli
ng
e a
l
.
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
due
o
he nea
l
y
li
nea a
li
gn
m
en
o a
o
ms
B
HO and a
s
a
con
s
equence,
he hyd ogen a
o
m
ha
s
a ocu
s
i
ng e ec
o
he
pho
oe
l
ec
on wa e.
Fi
gu e 5 a d
i
s
p
l
ay
s
he expe
i
m
en
a
l
s
pec
u
m
and
i
s
fi
u
s
i
ng a
s
a
m
ode
l
s
uc
u e c
l
u
s
e ‘‘c’’ o
Fi
g. 1. In
Fi
g. 5 b ,
he pha
s
e-co ec
ed
F
ou
i
e
an
s
o
m
F
T a
l
ong w
i
h
i
s
fi
a e p
l
o
ed. A
s
u
mm
a y o
he
s
uc
u a
l
pa a
m
e
e
s
ob
a
i
ned
i
n
he
fi
p ocedu e
i
s s
hown
i
n
he ‘‘expe
i
m
en
a
l
’’ a
m
e o
Tab
l
e I. A
s s
een
i
n
he
ab
l
e,
he a
l
ue
s
co
m
pa e we
ll
w
i
h
expe
i
m
en
a
l
e
s
u
l
s
ob
a
i
ned by o
he au
ho
s
.
M
u
l i
e
l
ec
on
exc
i
a
i
on
s
a e expec
ed a ound 5, 7.3, and 8.22 Å 1.38 They
can be de
ec
ed expe
i
m
en
a
ll
y
i
he d
i
e ence
s
pec
u
m
be
ween expe
i
m
en
a
l
s
pec
u
m
and
fi
exh
i
b
i
s
peak
s
ap-
p ox
i
m
a
e
l
y a
he
i
nd
i
ca
ed k- a
l
ue
s
. Th
i
s
i
s
no
he ca
s
e,
and
he e o e
m
u
l i
e
l
ec
on exc
i
a
i
on
s
we e no
i
nc
l
uded
i
n
he ana
l
y
s
i
s
.
S
o
m
e au
ho
s s
udy
i
ng b o
m
i
de conc
l
uded
ha
m
u
l i
e
l
ec
on exc
i
a
i
on
s
we e no
i
m
po
an
,38,41 wh
il
e o
h-
e
s
eached a h
i
ghe e
s
i
m
a
e o
m
u
l i
e
l
ec
on exc
i
a
i
on
s
and
eco
mm
ended
he
i
i
nc
l
u
s
i
on
i
n
he da
a ana
l
y
s
i
s
.45,46
The ac
ili
y
o hand
l
e
i
ndependen
s
uc
u a
l i
n o
m
a
i
on
o
s
a
i
s
i
ca
l
na
u e on
he
s
y
s
e
m
unde
s
udy enab
l
e
s
u
s
o
unde
ake a
s
econd EXA
FS
da
a ana
l
y
s
i
s
wh
i
ch co e
s
pond
s
o
he co
m
pu
ed EXA
FS
s
pec
u
m
o
m
he
M
C
s
nap
s
ho
s
da
s
hed
li
ne
i
n
Fi
g. 4 . Th
i
s
ype o
s
a
egy ha
s
a
l
eady been
pe o
m
ed
i
n p e
i
ou
s
wo k
s
dea
li
ng w
i
h ca
i
on
hyd a
i
on.22,25 A
fi
s
s
i
gh
,
h
i
s
cou
l
d be en
i
s
aged a
s
an
unna
u a
l
p ocedu e
o ob
a
i
n
he
s
uc
u a
l i
n o
m
a
i
on, a
s
he d
i
ec
exa
m
i
na
i
on o d
i
s
i
bu
i
on unc
i
on
s
de
i
ed o
m
M
C
s
ee
ms
o o e a
m
o e d
i
ec
way
o do
i
. Howe e ,
he
a p
i
o
i
know
l
edge o
he
s
uc
u a
l
e
s
u
l
s
g
i
e
s
u
s
an
i
dea
l
a
m
ewo k
o check
he u
s
ua
l
da
a ana
l
y
s
i
s
p ocedu e
o ex-
ac
h
i
s
i
n o
m
a
i
on o
m
an EXA
FS
s
pec
u
m
.
Fi
gu e
s
5 a
and 5 b
s
how
he co
m
pa
i
s
on be
ween
he
heo e
i
ca
ll
y
co
m
pu
ed
s
pec
u
m
and
i
s
fi
. The
fi
ed
s
pec
u
m
and
i
s
F
T
a e
i
n qu
i
e good ag ee
m
en
w
i
h
he
i
co e
s
pond
i
ng
heo-
e
i
ca
l
s
pec
a.
F
o
he pu po
s
e o
he
fi
,
s
i
ng
l
e
s
ca
e
i
ng
pa
h
s
B
O and
B
H and
he
m
u
l i
p
l
e
s
ca
e
i
ng pa
h
s
B
HO
and
B
HOH we e con
s
i
de ed. To educe
he nu
m
be o
fi
pa a
m
e
e
s
, a
ll
DW ac
o
s
o
he
B
O and
B
H pa
h
s
we e
a
ss
u
m
ed
o be
i
den
i
ca
l
, a
s s
ugge
s
ed by
he
s
i
m
u
l
a
i
on a
l
-
ue
s
(
B
O
20.055
i
n Tab
l
e I and
B
H
20.059). In
he ca
s
e o
he
heo e
i
ca
l
s
pec
u
m
,
he coo d
i
na
i
on nu
m
be wa
s
fi
xed
o
he
m
ean a
l
ue o
he
s
i
m
u
l
a
i
on. S0
2,
he a
m
p
li
ude educ-
i
on ac
o , wa
s s
e
o 1.
The ‘‘
heo e
i
ca
l
’’ a
l
ue
s
g
i
en
i
n Tab
l
e I a e a
ll
ob
a
i
ned
o
m
he
M
on
e
C
a
l
o
s
i
m
u
l
a
i
on e
s
u
l
s
. The ‘‘
M
C
s
i
m
u
l
a-
i
on’’
li
ne g
i
e
s
d
i
ec
e
s
u
l
s
co
m
pu
ed o
m
he
s
a
i
s
i
ca
l
s
i
m
u
l
a
i
on. ‘‘
Fi
o
heo e
i
ca
l
s
pec
u
m
’’ gene a
e
s
an
EXA
FS
s
pec
u
m
o
m
he
s
i
m
u
l
a
i
on
s
nap
s
ho
s
and
fi
s
h
i
s
s
pec
u
m
, u
s
i
ng o no
he
h
i
d o de cu
m
u
l
an
. The
s
e
wo
fi
s
un pa a
ll
e
l
o
he ‘‘
Fi
o expe
i
m
en
a
l
s
pec
u
m
,’’
he
m
a
i
n d
i
e ence be
i
ng
ha
he EXA
FS
unc
i
on ana
l
yzed
i
s
ha
ob
a
i
ned o
m
he
s
nap
s
ho
s
o
he
M
C
s
i
m
u
l
a
i
on.
In
he
ab
l
e,
he e
s
u
l
s
o
wo
fi
s
o
he
heo e
i
ca
l
s
pec
u
m
can be co
m
pa ed
:
he
fi
s
con
s
i
de
s
on
l
y cu
m
u-
l
an
s
up
o
s
econd o de ,
he
s
econd
i
nc
l
ude
s
he
h
i
d o de
cu
m
u
l
an
, wh
i
ch
i
s
con
s
a
i
ned w
i
h
he
s
econd o de cu
m
u-
l
an
a
l
ue by
fi
x
i
ng
he
s
kewne
ss
a
i
o3
/
(2)3
/
2]
o a
a
l
ue o 0.37. Th
i
s
nu
m
be a
i
s
e
s
o
m
he
s
i
m
u
l
a
i
on a
s
exp
l
a
i
ned be
l
ow. The d
i
e ence be
ween
he
fi
ed
B
O d
i
s
-
ance
s
a e w
i
h
i
n 0.1 Å due
o
he
i
n
oduc
i
on o
he
h
i
d
o de cu
m
u
l
an
. The
s
a
m
e p ocedu e pe o
m
ed on
he ex-
pe
i
m
en
a
l
s
pec
u
m
y
i
e
l
d
s s
i
m
il
a conc
l
u
s
i
on
s
.
C
o
m
pa ab
l
e
fi
nd
i
ng
s
we e ob
a
i
ned by D’Ange
l
oe
a
l
.
i
n a
s
udy o b o-
m
i
de
i
n
m
e
hano
l
.42
The d
i
s
ance
i
n
he
fi
o
he co
m
pu
ed
s
pec
u
m
i
s
0.1 Å
F
IG. 4.
C
o
m
pa
i
s
on o
he expe
i
m
en
a
l
s
o
li
d
li
ne and co
m
pu
ed
l
ong
da
s
hed
li
ne k2-we
i
gh
ed EXA
FS
unc
i
on. When H a
o
ms
a e no
i
nc
l
uded
a
s
back
s
ca
e e
s
,
he EXA
FS
unc
i
on wou
l
d be ep e
s
en
ed by
he
s
ho
da
s
hed
li
ne.
F
IG. 5. a Expe
i
m
en
a
l
EXA
FS
s
pec
u
m
and
i
s
be
s
fi
w
i
h
he pa a
m
-
e
e
s
i
nc
l
uded
i
n Tab
l
e I. b
P
ha
s
e-co ec
ed
F
ou
i
e
an
s
o
m
o
he
s
pec-
u
m
and
i
s
fi
.
6651
J
.
C
he
m
.
P
h
ys
.,
V
o
l
. 119,
N
o. 13, 1
O
c
obe
2003
B
o
mi
de h
y
d
a
i
on
s
u
c
u
e
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
l
a ge
han
he co e
s
pond
i
ng expe
i
m
en
a
l
one 3.44 e
s
u
s
3.34 . On one hand,
h
i
s
d
i
s
c epancy cou
l
d be a
s
c
i
bed
o
he
m
o
l
ecu
l
a po
en
i
a
l
m
ode
l
s
. On
he o
he hand,
he d
i
s
c ep-
ancy cou
l
d a
i
s
e o
m
he
fi i
ng p ocedu e
i
s
e
l
a
s
d
i
s
cu
ss
ed
be
l
ow.
C
.
An
alysis
o h
e
p
o
ce
du
e
o ob
ai
n
h
e
g
e
o
m
e
ical
p
a
a
m
e
e
s
o
m
a
non
i
g
i
d
d
is
i
bu
i
on
a
ound h
e
e
e
e
n
ce a
o
m
The EXA
FS
s
pec
u
m
o
he b o
m
i
de an
i
on
i
n wa
e
i
s
a
concep
ua
ll
y
i
n
e e
s
i
ng ca
s
e o
m
e
hodo
l
og
i
ca
l
s
ud
i
e
s
be-
cau
s
e
he
s
pec
u
m
i
s
do
m
i
na
ed by
he
B
O back
s
ca
e
i
ng
con
i
bu
i
on. The p e
s
en
s
udy co obo a
e
s
ha
con
i
bu-
i
on
s
o
m m
u
l i
p
l
e
s
ca
e
i
ng pa
h
s
excep
ed
he ‘‘ ocu
s
-
i
ng’’ pa
h
B
HO and
s
i
ng
l
e
s
ca
e
i
ng con
i
bu
i
on
s
o
m
a
o
ms
a
d
i
s
ance
s
l
a ge
han 5.0 Å p
l
ay a
m
i
no o
l
e.26,27
The
B
O d
i
s
i
bu
i
on o d
i
s
ance
s
i
s
, howe e , qu
i
e b oad
and a
s
y
mm
e
i
c. The e o e, a
m
ode
l
s
uc
u e
s
hou
l
d be
a
li
d,
i
i
wa
s
ab
l
e
o ep oduce e
ss
en
i
a
ll
y
he p obab
ili
y
d
i
s
i
bu
i
on unc
i
on o
he
B
O d
i
s
ance
s
. In
h
i
s s
ec
i
on,
he
ana
l
y
s
i
s
w
ill
be pe o
m
ed exc
l
u
s
i
e
l
y on
he
heo e
i
ca
ll
y
co
m
pu
ed
s
pec
u
m
,
s
o
ha
expe
i
m
en
a
l
con
s
i
de a
i
on
s
do
no
need
o be
aken
i
n
o accoun
and
he d
i
s
i
bu
i
on
i
s
known. The a
i
m
i
s
o
m
on
i
o
ho ough
l
y how
he EXA
FS
de
e
m
i
na
i
on can ep oduce
he geo
m
e
i
ca
l
d
i
s
i
bu
i
on,
wha
wa
s
u
s
ed e e
s
e
l
y
o gene a
e
he EXA
FS
s
pec
u
m
.
A
s
i
k
i
ng ea
u e o
he
s
uc
u a
l
de
e
m
i
na
i
on by
EXA
FS
s
pec
o
s
copy
i
s
ha
d
i
s
ance
s
a e u
s
ua
ll
y
s
li
gh
l
y
s
ho
e
han expec
ed, and
/
o ob
a
i
ned by o
he
echn
i
que
s
.1
S
uch a d
i
e ence
i
s
a
l
s
o ob
s
e ed be
ween
he d
i
s
ance ob-
a
i
ned by a e ag
i
ng
he
M
C
s
i
m
u
l
a
i
on
s
nap
s
ho
s
and
he
fi
ed d
i
s
ance
o
he
heo e
i
ca
l
s
pec
u
m
o exa
m
p
l
e,
R
B
O 3.54 e
s
u
s
3.44 Å . In ac
,
he coo d
i
na
i
on d
i
s
ance
ob
a
i
ned o
m
he EXA
FS fi i
s
nu
m
e
i
ca
ll
y e y c
l
o
s
e
o
he
m
ax
i
m
u
m
o
he g(
) unc
i
on
s
hown o
i
n
s
ance
i
n
R
e . 28.
Th
i
s
ob
s
e a
i
on app
li
e
s
a
l
s
o
o
he ca
s
e o
he
s
econd
s
he
ll
o
R
h3and
C
3.24,25 In
he b o
m
i
de
s
udy,
he
fi
ed DW
ac
o
s
a e on
l
y ough
l
y ha
l
o
he a
l
ue ound
i
n
he
s
i
m
u-
l
a
i
on 0.037 e
s
u
s
0.055 Å2), wh
il
e
he coo d
i
na
i
on nu
m
-
be
i
s m
a
i
n
a
i
ned
fi
xed. The
s
y
s
e
m
a
i
c unde e
s
i
m
a
i
on o
d
i
s
ance
s
e en when
he ‘‘co ec
’’
h
i
d o de cu
m
u
l
an
i
s
u
s
ed enab
l
e
s
a
s
li
gh
e
fi
ne
m
en
o
he e
s
i
m
a
ed expe
i
m
en-
a
l
d
i
s
ance ba
s
ed on a
an
s
e ab
ili
y o
he d
i
e ence ob-
a
i
ned o
m
he
heo e
i
ca
l
co
m
pu
a
i
on. Th
i
s s
hou
l
d be wa -
an
ed
i
he
s
hape o
he d
i
s
i
bu
i
on o
he
s
i
m
u
l
a
i
on
co e
s
pond
s
o
he ea
l
one,
R
heo RM
C
Si
m
u
l
a
i
on R
Fi
o
heo w
i
h3
3.54 3.44 Å 0.1 Å.
Then,
Rexp–
heo R
Fi
o exp w
i
h3R
heo 3.34 0.1 Å.
The e o e, ou e
s
i
m
a
e o
he a e age
fi
s
s
he
ll
B
O d
i
s
-
ance o
m
he expe
i
m
en
a
l
s
pec
u
m
i
s
3.44 0.07 Å.
In o de
o
fi
nd ou
m
o e abou
he ea
s
on
s
o
h
i
s
d
i
-
e ence
i
n
he
fi
s
hyd a
i
on
s
he
ll
,
s
e e a
l
a
e
m
p
s
we e
m
ade u
s
i
ng on
l
y
he
i
n o
m
a
i
on abou
he d
i
s
i
bu
i
on
i
n
h
i
s
s
he
ll
. The
s
uc
u a
l i
n o
m
a
i
on u
s
ed
i
n a
ll
he
s
e ca
l
cu
l
a-
i
on
s
i
s
ha
ob
a
i
ned o
m
he
M
C
e
s
u
l
s
. Tab
l
e I g
i
e
s
he
i
n
eg a
i
on nu
m
be , a e age
B
O d
i
s
ance and
i
s
DW ac
o
(2).
F
o
he pu po
s
e o
he ana
l
y
s
i
s
,
he
B
O
fi
s
peak had
o be
i
s
o
l
a
ed
s
o
m
ewha
a b
i
a
il
y,
s
i
nce
he d
i
s
i
bu
i
on
unc
i
on doe
s
no
d op
o ze o. The cho
s
en c
i
e
i
u
m
wa
s
o
u
s
e a
s
w
i
ch
i
ng unc
i
on, cen
e ed a ound
he
m
i
n
i
m
u
m
o
he d
i
s
i
bu
i
on unc
i
on,
ha
b
i
ng
s
he d
i
s
i
bu
i
on
o ze o
a c
angen
l
y be
ween 3.8 and 4.2 Å. I a
s
i
c
cu
o c
i
e-
i
u
m
i
s
cho
s
en
i
n
s
ead,
he qua
li
a
i
e conc
l
u
s
i
on
s
d awn
he e a e no
a ec
ed. The e e ence d
i
s
i
bu
i
on
i
n a
ll
he
s
e
ca
l
cu
l
a
i
on
s
i
s
g
i
en by
he p obab
ili
y d
i
s
i
bu
i
on unc
i
on
P
D
F
, p
l
o
ed
i
n
Fi
g. 6
s
o
li
d
li
ne . Th
i
s
unc
i
on
i
s
d
i
ec
l
y
e
l
a
ed
o
he ad
i
a
l
d
i
s
i
bu
i
on unc
i
on (g(R)),
P
D
F
R
B
O
N
g
s
wR
B
O R
B
O
2, 3
whe e
he
s
upe
s
c
i
p
‘‘
s
w’’ e e
s
o
he
s
w
i
ched g(R) and
N
i
s
a no
m
a
li
za
i
on con
s
an
.
TA
B
LE I.
B
e
s
fi
d
i
s
ance
s
, Debye–Wa
ll
e ac
o
s
, and coo d
i
na
i
on nu
m
be
s
a ound
he b o
m
i
de an
i
on
ob
a
i
ned o
m
he ana
l
y
s
i
s
o
he EXA
FS
s
pec
a and o
he
M
C
s
i
m
u
l
a
i
on u
s
i
ng 10 000
s
nap
s
ho
s
.
N
OR
B
O
/
Å
B
O
2
/
Å23
/
Å3
Expe
i
m
en
Fi
o expe
i
m
en
a
l
s
pec
u
m
5.84a3.27 0.04 0.035 0.002
Fi
o expe
i
m
en
a
l
s
pec
u
m
w
i
h30.37(
B
O
2)3
/
2
5.84a3.34 0.03 0.034 0.002 0.0023 0.0002
R
e . 26 7.2 0.4 3.36 0.01 0.027 0.002 0.0014 0.0006
R
e . 27 6.9 3.34 0.04 0.0065
R
e . 50 6a3.19 0.016
R
e . 48 6a3.20 0.022 0.0034
R
e . 41 5.1 0.5 3.29 0.04 0.026 0.03 0.0020 0.0020
Theo y
M
C
s
i
m
u
l
a
i
on 5.84 0.3 3.54 0.01 0.055 0.005 0.0036 0.0002
Fi
o
heo e
i
ca
l
s
pec
u
m
5.84a3.37 0.03 0.037 0.002
Fi
o
heo e
i
ca
l
s
pec
u
m
w
i
h30.37(
B
O
2)3
/
2
5.84a3.44 0.03 0.036 0.002 0.0025 0.0004
Fi
o 1
s
-
s
he
ll P
D
F
7.0 0.1 3.50 0.01 0.065 0.001
Fi
o 1
s
-
s
he
ll P
D
F
w
i
h36.9 0.1 3.54 0.01 0.058 0.001 0.0052 0.0005
a
Fi
xed a
l
ue.
6652
J
.
C
he
m
.
P
h
ys
.,
V
o
l
. 119,
N
o. 13, 1
O
c
obe
2003
M
e
kli
ng
e a
l
.
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
To o
ll
ow
he
s
ep
s
o an EXA
FS
da
a ana
l
y
s
i
s
,
he
F
ou-
i
e
an
s
o
m
o
he
P
D
F
wa
s
u
s
ed a
s
i
npu
o
he
fi
o
he
o
ll
ow
i
ng exp e
ss
i
on
:
47
P
D
F
k A exp
i
R
B
Ok2k2
/
2
i
3k3
/
6 4
wh
i
ch y
i
e
l
d
s
‘‘e ec
i
e cu
m
u
l
an
s
.’’ Tab
l
e I g
i
e
s
wo
s
e
s
o
e
s
u
l
s
, con
s
i
de
i
ng o no
he
h
i
d o de cu
m
u
l
an
. ‘‘
Fi
o
1
s
s
he
ll P
D
F
’’ u
s
e
s
he
B
O d
i
s
i
bu
i
on unc
i
on and
fi
s
coo d
i
na
i
on nu
m
be , d
i
s
ance, and DW ac
o
i
n a
m
anne
de
a
il
ed
i
n
he nex
s
ec
i
on. ‘‘
Fi
o 1
s
s
he
ll P
D
F
w
i
h3’’
add
i i
ona
ll
y
fi
s
he
h
i
d o de cu
m
u
l
an
. The
h
i
d o de
cu
m
u
l
an
i
s
ound
o be 0.0052 Å3
s
ee Tab
l
e I ,
ha
i
s
,
0.37( 2)3
/
2.
C
on
s
a
i
n
i
ng
he
s
kewne
ss
o a a
l
ue o 0.37
i
n
a
ll
he
fi
s
en
s
u e
s
ha
he d
i
s
i
bu
i
on
s
ound a e co
m
pa a-
b
l
y a
s
y
mm
e
i
ca
l
. Th
i
d o de cu
m
u
l
an
s
fi
na
ll
y d
i
e
g ea
l
y be
ween au
ho
s
and
m
e
hod
s
u
s
ed. A d
i
ec
fi
o
he
EXA
FS
s
pec
u
m
i
s s
ub
j
ec
o h
i
gh unce
a
i
n
i
e
s
:
Wa
ll
en
e
a
l
.26 de
e
m
i
ne a nega
i
e a
l
ue, wh
il
e
Si
m
one
e
a
l
.41
ob
a
i
n a a
l
ue
i
n ag ee
m
en
w
i
h
ho
s
e ob
a
i
ned by o
he
au
ho
s
u
s
i
ng a
l
e na
e app oache
s
.48 D’Ange
l
oe
a
l
.27 ob-
a
i
n a
s
kewne
ss
o 0.81. W
i
h
i
n
he
i
app oach, howe e ,
h
i
ghe o de cu
m
u
l
an
s
a
l
s
o p
l
ay a
s
i
gn
ifi
can
o
l
e. In
h
i
s
wo k, a d
i
ec
ca
l
cu
l
a
i
on o 3 o
m
he
M
C
s
i
m
u
l
a
i
on
y
i
e
l
d
s
0.0036,
ha
i
s
a
s
kewne
ss
o 0.28, bu
i
we wan
o
neg
l
ec
h
i
ghe o de cu
m
u
l
an
s
,
i i
s m
o e
i
n
e e
s
i
ng
o
m
ake u
s
e o an e ec
i
e a
l
ue.
When
s
econd and
h
i
d o de cu
m
u
l
an
s
a e
i
nc
l
uded,
he
a e age d
i
s
ance de
e
m
i
ned
i
n
he
fi
o
he
P
D
F i
s
equa
l
o
he e e ence one 3.54 Å . The co e
s
pond
i
ng d
i
s
i
bu
i
on
i
s
p
l
o
ed
i
n
Fi
g. 6 do
ed
li
ne . When
he
fi i
nc
l
ude
s
on
l
y
s
econd o de cu
m
u
l
an
s
,
he d
i
s
ance de
e
m
i
ned
i
s
3.50 Å
l
ong da
s
hed
li
ne . Tha
i
s
, a
s
ho
en
i
ng o
he d
i
s
ance
i
s
ob
s
e ed. Th
i
s
a
l
ue
i
s
qu
i
e d
i
e en
o
m
he one ob
a
i
ned
by
fi i
ng
o
he co
m
pu
ed EXA
FS
unc
i
on 3.44 o 3.37 Å,
e
s
pec
i
e
l
y .
Ano
he
e
s
o
he
m
e
hod o
he de
e
m
i
na
i
on o
he
s
uc
u e
li
e
s
i
n
he
i
n e
s
i
ga
i
on o
he po
ss
i
b
l
e a
i
ac
a
s
-
s
oc
i
a
ed
o
he gene a
i
on o
he EXA
FS
unc
i
on
i
a
he
F
E
FF/F
E
FF
IT
m
e
hod o
m
he
s
nap
s
ho
s
o
he
M
C
s
i
m
u
l
a-
i
on. Two nu
m
e
i
ca
l
exa
m
i
na
i
on
s
ha e been de
s
i
gned. The
fi
s
con
s
i
s
ed
i
n gene a
i
ng a
heo e
i
ca
l
EXA
FS
s
pec
u
m
a
i
s
i
ng
s
o
l
e
l
y o
m s
i
ng
l
e
s
ca
e
i
ng con
i
bu
i
on
s
o
he
fi
s
s
he
ll
o oxygen a
o
ms
. The
fi i
nc
l
uded on
l
y
B
O
s
i
ng
l
e
s
ca
-
e
i
ng pa
h
s
and
s
econd o de cu
m
u
l
an
s
, y
i
e
l
d
i
ng a d
i
s
ance
o 3.36 Å. The
s
econd exa
m
i
na
i
on wa
s
he gene a
i
on o an
EXA
FS
s
pec
u
m
ba
s
ed on
m
ode
l
s
uc
u e
s
o
he geo
m
e
y
‘‘c’’ o
Fi
g. 1, whe e
he po
s
i i
on o
he wa
e
m
o
l
ecu
l
e
s
wa
s
s
y
mm
e
i
ca
ll
y
m
od
ifi
ed be
ween 2.8 and 4.2 Å o
he
B
O
d
i
s
ance. The
s
e
s
pec
a we e we
i
gh
ed by
he
P
D
F
o
he
fi
s
peak. Th
i
s
heo e
i
ca
l
s
pec
u
m
bea
s
a c
l
o
s
e e
s
e
m
b
l
ance
o
he one ob
a
i
ned by
he a e ag
i
ng o
s
pec
a o
m
M
C
s
nap-
s
ho
s
, and
he
fi
pa a
m
e
e
s
a e e y
s
i
m
il
a . Th
i
s
i
s
a
s
ong
i
nd
i
ca
i
on
ha
he ea
s
on o
he d
i
s
c epancy
i
s
no
due
o
m
u
l i
p
l
e
s
ca
e
i
ng e ec
s
o
he p e
s
ence o hyd ogen a
o
ms
c
l
o
s
e
o
he b o
m
i
de, bu
i
s
a
he
o be ound
i
n
he
s
hape o
he d
i
s
i
bu
i
on and
he
i
nab
ili
y
o ad
j
u
s
i
w
i
h DW ac
o
s
.
I
V
.
C
O
NCLUD
I
N
G
R
E
MARK
S
XANE
S
and EXA
FS
s
pec
a o
B
K
-edge o b o
m
i
de
i
n
wa
e we e ca
l
cu
l
a
ed o
m s
i
m
u
l
a
i
on
s
nap
s
ho
s
and,
i
n
he
ca
s
e o XANE
S
, quan
u
m
-
m
echan
i
ca
ll
y
m
i
n
i
m
i
zed c
l
u
s
e
s
we e a
l
s
o p obed. Whe ea
s
he quan
u
m
-
m
echan
i
ca
l
c
l
u
s
e
s
do no
co
m
pa e we
ll
w
i
h expe
i
m
en
a
l
da
a
i
n
s
o
l
u
i
on,
he
s
e
o
s
i
m
u
l
a
i
on da
a
l
ead
s
o a good ag ee
m
en
. The d
i
s
-
c epanc
i
e
s
be
ween XANE
S
s
pec
a ca
l
cu
l
a
ed o
m
quan
u
m
-
m
echan
i
ca
l
s
uc
u e
s
and
M
C
s
i
m
u
l
a
i
on
s s
ugge
s
he need o
i
nc
l
ud
i
ng
s
a
i
s
i
ca
l i
n o
m
a
i
on
i
n
he co
m
pu-
a
i
on. In
h
i
s s
en
s
e,
i i
s
e
ss
en
i
a
l
o u
s
e a
s
a
i
s
i
ca
l
d
i
s
i
-
bu
i
on o wa
e
m
o
l
ecu
l
e
s
a ound
he b o
m
i
de an
i
on de
i
ed
o
m
a conden
s
ed
m
a
e
s
y
s
e
m
whe e
i
on–wa
e and
wa
e –wa
e
i
n
e ac
i
on
s
p
l
ay a
s
i
gn
ifi
can
o
l
e.
B
ea
i
ng
i
n
m
i
nd
ha
i
n
e
m
o
l
ecu
l
a po
en
i
a
l
s
we e
fi
ed
oab
i
n
i i
o
ca
l
cu
l
a
i
on
s
o
s
i
m
il
a
l
e e
l
han
ho
s
e u
s
ed o
he
s
uc
u e
op
i
m
i
zed quan
u
m
-
m
echan
i
ca
ll
y,
he
m
a
i
n ea
s
on
o
j
u
s
i
y
he d
i
e ence
m
u
s
be
he
s
a
i
s
i
ca
l
ac
o
s
.
In
he ca
s
e o
he EXA
FS
co
m
pu
a
i
on
s
o b o
m
i
de hy-
d a
i
on,
he
m
a
i
n con
i
bu
i
on
s
a e due
o
s
i
ng
l
e
s
ca
e
i
ng
o
m
he
fi
s
hyd a
i
on
s
he
ll
and, due
o
h
i
s
ea
s
on, can be
hand
l
ed ea
li
s
i
ca
ll
y by a one-d
i
m
en
s
i
ona
l
d
i
s
i
bu
i
on o
m
ode
l
s
uc
u e
s
. Th
i
s
i
s
a
s
i
m
p
lifi
ed p
i
c
u e o
he
m
o e
ea
li
s
i
c
s
ca
e
i
ng pheno
m
enon whe e
B
HO pa
h
s
and
B
H
pa
h
s
a e be
i
ng con
s
i
de ed.
The b oad and a
s
y
mm
e
i
c d
i
s
i
bu
i
on o
B
O d
i
s
ance
s
i
n
he
s
i
m
u
l
a
i
on wa
s
de
s
c
i
bed
i
n
e
ms
o an a
s
y
mm
e
y
pa a
m
e
e o 0.37
s
kewne
ss
i
n o de
o be ab
l
e
o ob
a
i
n
s
econd and
h
i
d o de cu
m
u
l
an
s
w
i
h
l
ow
i
nde
e
m
i
na
i
on
s
o
he
fi
o
he EXA
FS
s
pec
u
m
. Th
i
s
a
s
y
mm
e
y pa a
m
-
e
e wa
s
ob
a
i
ned by
fi i
ng
he
B
O d
i
s
i
bu
i
on o
he
s
i
m
u-
l
a
i
on
i
nk-
s
pace.
The d
i
s
c epanc
i
e
s
ha
appea be
ween
he
heo e
i
ca
l
EXA
FS
s
pec
u
m
and
i
s
fi
u
s
i
ng cu
m
u
l
an
s
i
nd
i
ca
e
ha
s
y
s
e
ms
w
i
h
s
i
gn
ifi
can
geo
m
e
i
ca
l
d
i
s
o de
i
n
he c
l
o
s
e
en
i
on
m
en
o
he ab
s
o be a
o
m
,
li
ke
he
fi
s
hyd a
i
on
s
he
ll
o
he b o
m
i
de an
i
on, can ha d
l
y be de
s
c
i
bed by cu-
m
u
l
an
s
li
m
i
ed
o
h
i
d o ou
h o de .49 Due
o
he cha -
ac
e
i
s
i
c
s
o
he p obab
ili
y d
i
s
i
bu
i
on unc
i
on, d
i
s
ance
s
ob
a
i
ned by a con en
i
ona
l fi
p ocedu e
o
he EXA
FS
s
pec-
u
m
a e ob
s
e ed
o be c
l
o
s
e
o
he
m
ax
i
m
u
m
o
he ad
i
a
l
d
i
s
i
bu
i
on unc
i
on when
s
o
l
e
l
y DW ac
o
s
a e con
s
i
de ed,
F
IG. 6.
B
O p obab
ili
y d
i
s
i
bu
i
on unc
i
on
s
P
D
F
o
m M
C
s
i
m
u
l
a
i
on
s
o
li
d
li
ne , o
m
fi
o
heo e
i
ca
l
EXA
FS
s
pec
u
m
w
i
h3da
s
hed , and
o
m
wo
fi
s
o
he
M
C
P
D
F:
w
i
h cu
m
u
l
an
s
up
o 2
l
ong da
s
hed and up
o 3 do
ed .
6653
J
.
C
he
m
.
P
h
ys
.,
V
o
l
. 119,
N
o. 13, 1
O
c
obe
2003
B
o
mi
de h
y
d
a
i
on
s
u
c
u
e
R
eu
s
e o
A
I
P
P
ub
lis
h
i
ng
c
on en
is
s
ub
j
e
c
o he e
ms
: h p
s
://pub
lis
h
i
ng.a
i
p.o
g/au ho
s
/
i
gh
s-
and
-
pe
missi
on
s
.
D
o
w
n
l
oaded o I
P
: 150.214.182.116
O
n:
W
ed, 19
O
c
2016 14:53:39
and a
l
s
o a
ll
s
ho
when
h
i
d o de cu
m
u
l
an
s
a e
i
n
o-
duced. The
s
y
s
e
m
a
i
c unde e
s
i
m
a
i
on o d
i
s
ance
s
e en
when
he ‘‘co ec
’’
h
i
d o de cu
m
u
l
an
i
s
u
s
ed enab
l
e
s
a
s
li
gh
e
fi
ne
m
en
o
he e
s
i
m
a
ed expe
i
m
en
a
l
d
i
s
ance. I
we a
ss
u
m
e
ha
he d
i
s
i
bu
i
on o d
i
s
ance
s
o
m
he
s
i
m
u-
l
a
i
on
i
s
co ec
, we ob
a
i
n
ha
he a e age
B
O d
i
s
ance
de
e
m
i
ned
i
n
he expe
i
m
en
a
l fi
3.34 Å
i
s
unde e
s
i
m
a
ed
by 0.1 Å. The e o e, ou be
s
gue
ss
o
he expe
i
m
en
a
l
d
i
s
-
ance
i
s
3.44 0.07 Å. A co
m
b
i
na
i
on o expe
i
m
en
a
l
and
heo e
i
ca
l
da
a ana
l
y
s
i
s
g
i
e
s
w
i
de po
ss
i
b
ili i
e
s
o
i
n e
s
i
-
ga
e
he geo
m
e
i
ca
l
p ope
i
e
s
o
s
y
s
e
ms
p e
s
en
i
ng
ill
-
de
fi
ned
s
uc
u a
l
pa
e n
s
.
ACKN
O
WL
E
D
G
M
E
NT
S
The au
ho
s
hank D . A.
M
un
˜
oz-
P
a
´ez o he expe
i
-
m
en
a
l
co
ll
abo a
i
on and he he
l
p u
l
d
i
s
cu
ss
i
on
s
.
S
ugge
s
-
i
on
s
o
m
he e e ee ha e
i
m
p o ed
h
i
s
pape .
P
a
i
ck
M
e -
k
li
ng w
i
s
he
s
o
hank
he
J
un
a de Anda
l
uc
ı
´a and
he
Deu
s
che
F
o
s
chung
s
ge
m
e
i
n
s
cha
o
fi
nanc
i
a
l
s
uppo
. Ex-
pe
i
m
en
a
l
s
pec
a we e
m
ea
s
u ed unde p opo
s
a
l
95G-215
o
he
P
ho
on
F
ac
o y, T
s
ukuba,
J
apan.
F
undac
i
o
´n
R
a
m
o
´n
A ece
s
XI
C
oncu
s
o Nac
i
ona
l i
s
acknow
l
edged o
fi
nan-
c
i
a
l
s
uppo
.
1H. Oh
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