A multi-crystal wavelength dispersive hard x-ray spectrometer with high-energy resolution and large solid angle collection is described. The instrument is specifically designed for time-resolved applications of x-ray emission spectroscopy (XES) and x-ray Raman scattering (XRS) at X-ray Free Electron Lasers (XFEL) and synchrotron radiation facilities. It also simplifies resonant inelastic x-ray scattering (RIXS) studies of the whole 2d RIXS plane. The spectrometer is based on the Von Hamos geometry. This dispersive setup enables an XES or XRS spectrum to be measured in a single-shot mode, overcoming the scanning needs of the Rowland circle spectrometers. In conjunction with the XFEL temporal profile and high-flux, it is a powerful tool for studying the dynamics of time-dependent systems. Photo-induced processes and fast catalytic reaction kinetics, ranging from femtoseconds to milliseconds, will be resolvable in a wide array of systems circumventing radiation damage.

1.
J.
Arthur
,
G.
Materlik
,
R.
Tatchyn
, and
H.
Winick
, “
The LCLS - A 4th-generation light-source using the SLAC linac
,”
Rev. Sci. Instrum.
66
(
2
),
1987
1989
(
1995
).
2.
P.
Emma
,
R.
Akre
,
J.
Arthur
,
R.
Bionta
,
C.
Bostedt
,
J.
Bozek
,
A.
Brachmann
,
P.
Bucksbaum
,
R.
Coffee
,
F. J.
Decker
,
Y.
Ding
,
D.
Dowell
,
S.
Edstrom
,
A.
Fisher
,
J.
Frisch
,
S.
Gilevich
,
J.
Hastings
,
G.
Hays
,
P.
Hering
,
Z.
Huang
,
R.
Iverson
,
H.
Loos
,
M.
Messerschmidt
,
A.
Miahnahri
,
S.
Moeller
,
H. D.
Nuhn
,
G.
Pile
,
D.
Ratner
,
J.
Rzepiela
,
D.
Schultz
,
T.
Smith
,
P.
Stefan
,
H.
Tompkins
,
J.
Turner
,
J.
Welch
,
W.
White
,
J.
Wu
,
G.
Yocky
, and
J.
Galayda
, “
First lasing and operation of an angstrom-wavelength free-electron laser
,”
Nat. Photonics
4
(
9
),
641
647
(
2010
).
3.
P.
Glatzel
and
U.
Bergmann
, “
High resolution 1s core hole x-ray spectroscopy in 3d transition metal complexes - electronic and structural information
,”
Coord. Chem. Rev.
249
(
1–2
),
65
95
(
2005
).
4.
U.
Bergmann
,
P.
Glatzel
, and
S. P.
Cramer
, “
Bulk-sensitive XAS characterization of light elements: From x-ray Raman scattering to x-ray Raman spectroscopy
,”
Microchem. J.
71
(
2–3
),
221
230
(
2002
).
5.
J.
Nordgren
,
G.
Bray
,
S.
Cramm
,
R.
Nyholm
,
J. E.
Rubensson
, and
N.
Wassdahl
, “
Soft-x-ray emission-spectroscopy using monochromatized synchrotron radiation
,”
Rev. Sci. Instrum.
60
(
7
),
1690
1696
(
1989
).
6.
A.
Kotani
and
S.
Shin
, “
Resonant inelastic x-ray scattering spectra for electrons in solids
,”
Rev. Mod. Phys.
73
(
1
),
203
246
(
2001
).
7.
L. J. P.
Ament
,
M.
van Veenendaal
,
T. P.
Devereaux
,
J. P.
Hill
, and
J.
van den Brink
, “
Resonant inelastic x-ray scattering studies of elementary excitations
,”
Rev. Mod. Phys.
83
(
2
),
705
767
(
2011
).
8.
A.
Nilsson
and
L. G. M.
Pettersson
, “
Chemical bonding on surfaces probed by x-ray emission spectroscopy and density functional theory
,”
Surf. Sci. Rep.
55
(
2–5
),
49
167
(
2004
).
9.
U.
Bergmann
and
P.
Glatzel
, “
X-ray emission spectroscopy
,”
Photosynth. Res.
102
(
2–3
),
255
266
(
2009
).
10.
J.
Messinger
,
J. H.
Robblee
,
U.
Bergmann
,
C.
Fernandez
,
P.
Glatzel
,
H.
Visser
,
R. M.
Cinco
,
K. L.
McFarlane
,
E.
Bellacchio
,
S. A.
Pizarro
,
S. P.
Cramer
,
K.
Sauer
,
M. P.
Klein
, and
V. K.
Yachandra
, “
Absence of Mn-centered oxidation in the S2 > S3 transition: Implications for the mechanism of photosynthetic water oxidation
,”
J. Am. Chem. Soc.
123
(
32
),
7804
7820
(
2001
).
11.
Y.
Pushkar
,
X.
Long
,
P.
Glatzel
,
G. W.
Brudvig
,
G. C.
Dismukes
,
T. J.
Collins
,
V. K.
Yachandra
,
J.
Yano
, and
U.
Bergmann
, “
Direct detection of oxygen ligation to the Mn4Ca cluster of photosystem II by x-ray emission spectroscopy
,”
Angew. Chem., Int. Ed.
49
(
4
),
800
803
(
2010
).
12.
K. M.
Lancaster
,
M.
Roemelt
,
P.
Ettenhuber
,
Y. L.
Hu
,
M. W.
Ribbe
,
F.
Neese
,
U.
Bergmann
, and
S.
DeBeer
, “
X-ray emission spectroscopy evidences a central carbon in the nitrogenase iron-molybdenum cofactor
,”
Science
334
(
6058
),
974
977
(
2011
).
13.
U.
Bergmann
,
M. M.
Grush
,
C. R.
Horne
,
P.
DeMarois
,
J. E.
Penner-Hahn
,
C. F.
Yocum
,
D. W.
Wright
,
C. E.
Dube
,
W. H.
Armstrong
,
G.
Christou
,
H. J.
Eppley
, and
S. P.
Cramer
, “
Characterization of the Mn oxidation states in photosystem II by K beta x-ray fluorescence spectroscopy
,”
J. Phys. Chem. B
102
(
42
),
8350
8352
(
1998
).
14.
H.
Visser
,
E.
Anxolabehere-Mallart
,
U.
Bergmann
,
P.
Glatzel
,
J. H.
Robblee
,
S. P.
Cramer
,
J. J.
Girerd
,
K.
Sauer
,
M. P.
Klein
, and
V. K.
Yachandra
, “
MnK-edge XANES and K beta XES studies of two Mn-oxo binuclear complexes: Investigation of three different oxidation states relevant to the oxygen-evolving complex of photosystem II
,”
J. Am. Chem. Soc.
123
(
29
),
7031
7039
(
2001
).
15.
P.
Glatzel
,
J.
Singh
,
K. O.
Kvashnina
, and
J. A.
van Bokhoven
, “
In situ characterization of the 5d density of states of Pt nanoparticles upon adsorption of CO
,”
J. Am. Chem. Soc.
132
(
8
),
2555
(
2010
).
16.
M. A.
Beckwith
,
M.
Roemelt
,
M. N.
Collomb
,
C.
DuBoc
,
T. C.
Weng
,
U.
Bergmann
,
P.
Glatzel
,
F.
Neese
, and
S.
DeBeer
, “
Manganese K beta x-ray emission spectroscopy as a probe of metal-ligand interactions
,”
Inorg. Chem.
50
(
17
),
8397
8409
(
2011
).
17.
G.
Smolentsev
,
A. V.
Soldatov
,
J.
Messinger
,
K.
Merz
,
T.
Weyhermuller
,
U.
Bergmann
,
Y.
Pushkar
,
J.
Yano
,
V. K.
Yachandra
, and
P.
Glatzel
, “
X-ray emission spectroscopy to study ligand valence orbitals in Mn coordination complexes
,”
J. Am. Chem. Soc.
131
(
36
),
13161
13167
(
2009
).
18.
N.
Lee
,
T.
Petrenko
,
U.
Bergmann
,
F.
Neese
, and
S.
DeBeer
, “
Probing valence orbital composition with iron K beta x-ray emission spectroscopy
,”
J. Am. Chem. Soc.
132
(
28
),
9715
9727
(
2010
).
19.
U.
Bergmann
,
C. R.
Horne
,
T. J.
Collins
,
J. M.
Workman
, and
S. P.
Cramer
, “
Chemical dependence of interatomic x-ray transition energies and intensities—A study of Mn K beta and K beta(2,5) spectra
,”
Chem. Phys. Lett.
302
(
1–2
),
119
124
(
1999
).
20.
J. F.
Lin
,
H.
Watson
,
G.
Vanko
,
E. E.
Alp
,
V. B.
Prakapenka
,
P.
Dera
,
V. V.
Struzhkin
,
A.
Kubo
,
J. Y.
Zhao
,
C.
McCammon
, and
W. J.
Evans
, “
Intermediate-spin ferrous iron in lowermost mantle post-perovskite and perovskite
,”
Nat. Geosci.
1
(
10
),
688
691
(
2008
).
21.
R. A.
Mori
,
E.
Paris
,
G.
Giuli
,
S. G.
Eeckhout
,
M.
Kavcic
,
M.
Zitnik
,
K.
Bucar
,
L. G. M.
Pettersson
, and
P.
Glatzel
, “
Sulfur-metal orbital hybridization in sulfur-bearing compounds studied by x-ray emission spectroscopy
,”
Inorg. Chem.
49
(
14
),
6468
6473
(
2010
).
22.
R. A.
Mori
,
E.
Paris
,
G.
Giuli
,
S. G.
Eeckhout
,
M.
Kavcic
,
M.
Zitnik
,
K.
Bucar
,
L. G. M.
Pettersson
, and
P.
Glatzel
, “
Electronic structure of sulfur studied by x-ray absorption and emission spectroscopy
,”
Anal. Chem.
81
(
15
),
6516
6525
(
2009
).
23.
G.
Vanko
,
P.
Glatzel
,
V. T.
Pham
,
R.
Abela
,
D.
Grolimund
,
C. N.
Borca
,
S. L.
Johnson
,
C. J.
Milne
, and
C.
Bressler
, “
Picosecond time-resolved x-ray emission spectroscopy: Ultrafast spin-state determination in an iron complex
,”
Angew. Chem., Int. Ed.
49
(
34
),
5910
5912
(
2010
).
24.
H. H.
Johann
,
Z. Phys.
69
,
185
(
1931
).
25.
T.
Johansson
,
Z. Phys.
82
,
507
(
1933
).
26.
V.
Stojanoff
,
K.
Hamalainen
,
D. P.
Siddons
,
J. B.
Hastings
,
L. E.
Berman
,
S.
Cramer
, and
G.
Smith
, “
A high-resolution x-ray-fluorescence spectrometer for near-edge absorption studies
,”
Rev. Sci. Instrum.
63
(
1
),
1125
1127
(
1992
).
27.
X.
Wang
,
M. M.
Grush
,
A. G.
Froeschner
, and
S. P.
Cramer
, “
High-resolution x-ray fluorescence and excitation spectroscopy of metalloproteins
,”
J. Synchrotron Radiat.
4
,
236
242
(
1997
)
28.
U.
Bergmann
and
S. P.
Cramer
, “
A high-resolution large-acceptance analyzer for x-ray fluorescence and Raman spectroscopy
,”
Proc. SPIE
3448
,
198
209
(
1998
).
29.
P.
Glatzel
,
F. M. F.
de Groot
, and
U.
Bergmann
, “
Hard x-ray photon-in photon-out spectroscopy
,”
Synchrotron Radiat. News
22
(
2
),
12
16
(
2009
).
30.
I.
Llorens
,
E.
Lahera
,
W.
Delnet
,
O.
Proux
,
A.
Braillard
,
J. L.
Hazemann
,
A.
Prat
,
D.
Testemale
,
F.
Gelebart
,
M.
Morand
,
A.
Shukla
,
N.
Bardou
,
O.
Ulrich
,
S.
Arnaud
,
J. F.
Berar
,
N.
Boudet
,
B.
Caillot
,
P.
Chaurand
,
J.
Rose
,
E.
Doelsch
,
P.
Martin
, and
P. L.
Solari
, “
High energy resolution five-crystal spectrometer for high quality fluorescence and absorption measurements on an x-ray absorption spectroscopy beamline
,”
Rev. Sci. Instrum.
83
(
6
),
9
(
2012
).
31.
D.
Sokaras
,
D.
Nordlund
,
T. C.
Weng
,
Alonso-R.
Mori
,
P.
Velikov
,
D.
Wagner
,
A.
Garachtchenko
,
M.
George
,
V.
Borzenets
,
B.
Johnson
,
T.
Rabedeau
, and
U.
Bergmann
, “
A high resolution and large solid angle x-ray Raman spectroscopy end-station at the Stanford Synchrotron Radiation Lightsource
,”
Rev. Sci. Instrum.
83
(
4
),
043112
(
2012
).
32.
E.
Kleymenov
,
J. A.
van Bokhoven
,
C.
David
,
P.
Glatzel
,
M.
Janousch
,
R.
Alonso-Mori
,
M.
Studer
,
M.
Willimann
,
A.
Bergamaschi
,
B.
Henrich
, and
M.
Nachtegaal
, “
Five-element Johann-type x-ray emission spectrometer with a single-photon-counting pixel detector
,”
Rev. Sci. Instrum.
82
(
6
),
065107
(
2011
).
33.
Q.
Qian
,
T. A.
Tyson
,
W. A.
Caliebe
, and
C. C.
Kao
, “
High-efficiency high-energy-resolution spectrometer for inelastic x-ray scattering
,”
J. Phys. Chem. Solids
66
(
12
),
2295
2298
(
2005
).
34.
R.
Verbeni
,
M.
Kocsis
,
S.
Huotari
,
M.
Krisch
,
G.
Monaco
,
F.
Sette
, and
G.
Vanko
, “
Advances in crystal analyzers for inelastic x-ray scattering
,”
J. Phys. Chem. Solids
66
(
12
),
2299
2305
(
2005
).
35.
P.
Glatzel
,
U.
Bergmann
,
W. W.
Gu
,
H. X.
Wang
,
S.
Stepanov
,
B. S.
Mandimutsira
,
C. G.
Riordan
,
C. P.
Horwitz
,
T.
Collins
, and
S. P.
Cramer
, “
Electronic structure of Ni complexes by x-ray resonance Raman spectroscopy (resonant inelastic x-ray scattering)
,”
J. Am. Chem. Soc.
124
(
33
),
9668
9669
(
2002
).
36.
M.
Kavcic
,
M.
Zitnik
,
K.
Bucar
,
A.
Mihelic
,
M.
Stuhec
,
J.
Szlachetko
,
W.
Cao
,
R. A.
Mori
, and
P.
Glatzel
, “
Separation of two-electron photoexcited atomic processes near the inner-shell threshold
,”
Phys. Rev. Lett.
102
(
14
),
143001
(
2009
).
37.
B.
Dickinson
,
G. T.
Seidler
,
Z. W.
Webb
,
J. A.
Bradley
,
K. P.
Nagle
,
S. M.
Heald
,
R. A.
Gordon
, and
I. M.
Chou
, “
A short working distance multiple crystal x-ray spectrometer
,”
Rev. Sci. Instrum.
79
(
12
),
123112
(
2008
).
38.
L. v.
Hamos
, “
Rontgenspektroskopie und Abbildung mittels gekrummter kristallreflektoren
,”
Naturwiss.
20
,
705
706
(
1932
).
39.
J.
Hoszowska
, and
J. C.
Dousse
, “
High-resolution XES and RIXS studies with a von Hamos Bragg crystal spectrometer
,”
J. Electron Spectrosc. Relat. Phenom.
137
,
687
690
(
2004
).
40.
H.
Hayashi
,
M.
Kawata
,
R.
Takeda
,
Y.
Udagawa
,
Y.
Watanabe
,
T.
Takano
,
S.
Nanao
, and
N.
Kawamura
, “
A multi-crystal spectrometer with a two-dimensional position-sensitive detector and contour maps of resonant K beta emission in Mn compounds
,”
J. Electron Spectrosc. Relat. Phenom.
136
(
1–2
),
191
197
(
2004
).
41.
R.
Alonso-Mori
and
P.
Glatzel
RT4XES; see https://sites.google.com/site/rt4xes/
42.
M.
Krisch
, Ph.D. dissertation.
Dortmund University
,
1993
.
43.
S.
Takagi
, “
Dynamical theory of diffraction applicable to crystals with any kind of small distortion
,”
Acta Crystallogr.
15
(
12
),
1311
1312
(
1962
).
44.
D.
Taupin
, “
Théorie dynamique de la diffraction des rayons X par les cristaux déformés
,”
Bull. Soc. Fr. Mineral. Cristallogr.
87
,
469
(
1964
).
45.
S.
Hayakawa
,
A.
Yamaguchi
,
W.
Hong
,
Y.
Gohshi
,
T.
Yamamoto
,
K.
Hyashi
,
J.
Kawai
, and
S.
Goto
, “
A wavelength dispersive x-ray spectrometer for small area x-ray fluorescence spectroscopy at SPring-8 BL39XU
,”
Spectrochim. Acta, Part B
54
(
171
),
171
177
(
1999
).
46.
J.
Yano
,
J.
Kern
,
K. D.
Irrgang
,
M. J.
Latimer
,
U.
Bergmann
,
P.
Glatzel
,
Y.
Pushkar
,
J.
Biesiadka
,
B.
Loll
,
K.
Sauer
,
J.
Messinger
,
A.
Zouni
, and
V. K.
Yachandra
, “
X-ray damage to the Mn4Ca complex in single crystals of photosystem II: A case study for metalloprotein crystallography
,”
Proc. Natl. Acad. Sci. U.S.A.
102
(
34
),
12047
12052
(
2005
).
47.
Y.
Mizuno
and
Y.
Ohmura
, “
Theory of x-ray Raman scattering
,”
J. Phys. Soc. Jpn.
22
(
2
),
445
(
1967
).
48.
T.
Suzuki
, “
X-ray Raman scattering experiment. I
.,”
J. Phys. Soc. Jpn.
22
(
5
),
1139
(
1967
).
49.
W.
Schulke
,
A.
Berthold
,
A.
Kaprolat
, and
H. J.
Guntherodt
, “
Evidence for interlayer band shifts upon lithium Intercalation in graphite from inelastic X-ray-scattering
,”
Phys. Rev. Lett.
60
(
21
),
2217
2220
(
1988
).
50.
H.
Nagasawa
,
S.
Mourikis
, and
W.
Schulke
, “
X-ray Raman spectrum of Li, Be, and graphite in a high-resolution inelastic synchrotron x-ray-scattering experiment
,”
J. Phys. Soc. Jpn.
58
(
2
),
710
717
(
1989
).
51.
K.
Tohji
and
Y.
Udagawa
, “
X-ray Raman-scattering as a substitute for soft-x-ray-absorption fine-structure
,”
Phys. Rev. B
39
(
11
),
7590
7594
(
1989
).
52.
N.
Watanabe
,
H.
Hayashi
,
Y.
Udagawa
,
K.
Takeshita
, and
H.
Kawata
, “
Anisotropy of hexagonal boron nitride core absorption spectra by x-ray Raman spectroscopy
,”
Appl. Phys. Lett.
69
(
10
),
1370
1372
(
1996
).
53.
C.
Masciovecchio
,
U.
Bergmann
,
M.
Krisch
,
G.
Ruocco
,
F.
Sette
, and
R.
Verbeni
, “
A perfect crystal x-ray analyser with meV energy resolution
,”
Nucl. Instrum. Methods Phys. Res. B
111
(
1–2
),
181
186
(
1996
).
54.
P. A.
Montano
,
D. L.
Price
,
A. T.
Macrander
, and
B. R.
Cooper
, “
Inelastic x-ray scattering from 6H-SiC
,”
Phys. Rev. B
66
(
16
),
165218
(
2002
).
55.
B. C.
Larson
,
W.
Ku
,
J. Z.
Tischler
,
C.-C.
Lee
,
O. D.
Restrepo
,
A. G.
Eguiluz
,
P.
Zschack
, and
K. D.
Finkelstein
, “
Nonresonant inelastic x-ray scattering and energy-resolved Wannier function investigation of d-d excitations in NiO and CoO
,”
Phys. Rev. Lett.
99
(
2
),
026401
(
2007
).
You do not currently have access to this content.