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Ultrafast electronic dynamics in polyatomic molecules studied using femtosecond vacuum
ultraviolet and x-ray pulses

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2014 J. Phys. B: At. Mol. Opt. Phys. 47 124001(http://iopscience.iop.org/0953-4075/47/12/124001)
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Journal of Physics B: Atomic, Molecular and Optical Physics
J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001 (14pp)

doi:10.1088/0953-4075/47/12/124001

Review Article

Ultrafast electronic dynamics in polyatomic
molecules studied using femtosecond
vacuum ultraviolet and x-ray pulses
Toshinori Suzuki 1,2,3
1

Department of Chemistry, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan
Japan Science and Technology Agency, CREST, Sanbancho, Chiyoda-ku, Tokyo, 102-0075, Japan
3
RIKEN Center for Advanced Photonics, RIKEN, Wako, Saitama 351-0198, Japan2

E-mail: suzuki@kuchem.kyoto-u.ac.jp
Received 24 December 2013
Accepted for publication 25 March 2014
Published 10 June 2014
Abstract

Time-resolved velocity map photoelectron imaging is performed using sub-20 fs deep
ultraviolet and vacuum ultraviolet pulses to study electronic dynamics of isolated polyatomic
molecules. The non-adiabatic dynamics of pyrazine, furan and carbon disulfide (CS2) aredescribed as examples. Also described is sub-picosecond time-resolved x-ray direct absorption
spectroscopy using a hard x-ray free electron laser (SACLA) and a synchronous near
ultraviolet laser to study ultrafast electronic dynamics in solutions.
Keywords: ultrafast, photoelectron, ultraviolet, x-ray, molecule(Some figures may appear in colour only in the online journal)

synchrotron radiation facilities, HHG produces more than
three orders of magnitude shorter pulse durations, enabling
real-time observation of electronic dynamics. One of the
difficulties in using HHG for EUV spectroscopy remains inthe separation of single-order radiation from a comb-likestructure of odd-order harmonics (or an extremely broad
continuum), because multilayer mirrors with high reflectivity
are only available for limited wavelength regions such as
6–7, 13.5 or 30 nm. New techniques such as the timedelay-compensated monochromator improve the efficiency
and flexibility of wavelength separation. Thus, single-orderhigh harmonics is becoming a more convenient EUV lightsource for spectroscopic purposes. Interested readers may referto other articles in this special issue for details about the physics
and applications of HHG.
One of the weak points of HHG is rather low pulse
energy, typically tens of pJ after separation of a single order,
although technical improvements are continuing to increase
the pulse energy [4]. An alternative solution for generating
intense VUV radiation is non-resonant four-wave mixing infilamentation propagation. Typical output pulse energies for

1. Introduction
One of the keys for elucidating chemical reaction mechanisms
is observation of ultrafast electronic dynamics driving nuclear
motions in molecules. In these electronic dynamics, valence
electrons play central roles, which are most clearly observed
by ultrafast photoelectron spectroscopy using ultraviolet(UV) and vacuum ultraviolet (VUV) radiation. Inner-shellelectrons usually play only minor roles; however, they
exhibit characteristic chemical shifts of the electron binding
energies, depending on oxidation states and chemical bondingof individual atoms. X-ray radiation is indispensable forobserving these inner-shell electrons. Thus, ultrashort pulses
from deep UV to x-ray are valuable tools to study electronic
and chemical dynamics.
In the past decade, high harmonics generation (HHG)
has opened new avenues to attosecond science and extreme
UV (EUV) spectroscopy [1–3]. An HHG light source usinga Ti:sapphire laser (800 nm) generates photon energies up to
100 eV, while an intense infrared driving laser can produce
photons up to 1 keV. Compared to the third generation
0953-4075/14/124001+14$33.00

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J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article

the input pulse energies of 0.5 mJ (770 nm) + 0.5 mJ (390 nm)
are >10 μJ at 264 nm, >1 μJ at 198 nm, and >100 nJ at
159 nm [5–7]. Radiation at 130 nm has also been observed in
our laboratory. The method only requires temporal and spatial
overlap of intense femtosecond laser pulses in a rare gas cell.
In the cell, the laser pulses alter the local refractive index of
the gas and self-focus to cause ionization of the gas. Since
the ionized gas species reverses the spatial gradient of therefractive index with respect to that of the neutral gas, theoverall effect enables propagation of collimated laser beams
over the Rayleigh length. Even if each of the two-colour
laser pulses is not intense enough to create filamentation,
cooperative interaction between the two-colour fields and thegas medium can induce filamentation propagation [6]. The
intensity clamping and mode cleaning effects in filamentation
provide stable and spatially clean output pulses [8].
While filamentation four-wave mixing is a table-top VUVlight source, a free electron laser is a large-scale facility togenerate ultrashort and ultraintense pulses from the VUVto hard x-ray region [9–12]. There are already a number offree electron lasers around the world, such as FLASH (freeelectron LASer in Hamburg), SCSS (SPring-8 Compact SASE
source), LCLS (linac coherent light source), SACLA (Spring8 Angstrom compact free electron LAser) and FERMI (freeelectron laser radiation for multidisciplinary investigation).
(SASE stands for self-amplification of spontaneous emission.)
SCSS is the first VUV free electron laser in Japan, and its
central wavelength is 51–62 nm, although longer wavelengths
can be generated under special operation conditions. The pulse
energy from SCSS is as high as 30 μJ pulse−1 at 60 nm, which
is higher than that of HHG by orders of magnitudes. SACLA
is a much larger facility with the total length of 700 m, and it isoperated at a beam energy of 8.5 GeV. The photon energy range
is 4.5–15 keV. When synchronized with a femtosecond laser,
both SCSS and SACLA have timing jitter of several hundred
femtoseconds, inherent to SASE. Picosecond time resolution
can be obtained routinely, and subpicosecond time-resolution
is obtainable using measurement of individual pulse timing.
The severe limitations of free electron lasers based on using
normal-conducting linear accelerators are low repetition rates(10–100 Hz) and difficulty to perform multiple experiments
simultaneously, unlike synchrotron radiation facilities, owing
to the nature of a linear accelerator. Various technicalstrategies, such as electron beam steering into multiple beamlines, are being planned to overcome these problems [13].
Yabashi et al reported more details about atomic, molecularand optical physics experiments at SCSS and SACLA [14].
In this article, I describe our recent experiments performed
using VUV and x-ray radiation generated by filamentaion
four-wave mixing and SACLA, respectively. In section 2,
I describe sub-20 fs pulse generation in the deep UVand VUV regions by multi-colour filamentation four-wave
mixing. Time-resolved velocity map photoelectron imaging(TRPEI) of three molecules is discussed as applications of
this light source. Pyrazine provides an example as to how theexperimental study has progressed using both the filamentation
light source and a free electron laser. Furan provides anexample as to how theoretical simulation of TRPEI has

(a)

(b)

Figure 1. (a) Schematic diagram of our experimental setup forfilamentation four-wave mixing. (b) Schematic drawing of thedifferential pumping system. All dimensions are given in
millimeters. Reprinted with permission from [7]. © 2013 The
Optical Society of America.

been improved to enable simulation of photoelectron angular
distributions. CS2 is the last example to show how a VUV probe
pulse captures the entire wave packet motions in the excitedstate. In section 3, I discuss pump–probe x-ray absorption
spectroscopy using SACLA and a synchronous femtosecond
laser to study electronic dynamics in solution, in which adispersive spectrometer and a dual beam method are employed[15]. Section 4 provides a summary and outlook.
2. Sub-20 fs time-resolved velocity map
photoelectron imaging
2.1. Generation of multicolour sub-20 fs pulses byfilamentation four-wave mixing

Filamentation four-wave mixing enables generation ofultrashort pulses in the deep UV and VUV regions
simultaneously in a single rare gas cell. This single cell
scheme provides a simple optical setup with very precise andstable optical pump–probe delay. The generation scheme of
the multiple colours is cascaded four-wave mixing processes.
In our initial study [5], we demonstrated simultaneous
generation of only the third and fourth harmonics (3ω and 4ω,respectively). Although the fifth and sixth harmonics (5ω and6ω) must have been generated, the optical path was in air andnot transparent to VUV radiation. Our current experimental
setup has the entire optical paths under vacuum from thefilamentation cell to the target to use VUV radiation [7].
Figure 1(a) shows a schematic diagram of our apparatus. A
cryogenically cooled Ti:sapphire multipass amplifier delivers∼770 nm pulses (25 fs, 1.5 mJ) at 1 kHz. The fundamental
frequency pulse (ω) is split into two beams with a ratio of 3:7.
The higher intensity beam is converted to the second harmonic,
2ω, in a β-barium borate crystal (β-BBO, θ = 29◦ , t =0.3 mm). A dielectric concave mirror (r = 2,000 mm) focuses
the second harmonic into a neon gas cell through a Brewsterangled calcium fluoride (CaF2) window (t = 1 mm). This
concave mirror also separates the second harmonic from the2

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article

between the VUV and deep UV pulses is ca. 1◦ . The entire
optics chamber is evacuated using two turbo molecular pumps(300 L s−1) to maintain the pressure below 2 × 10−6 Torrwhen operating the filamentation gas cell. The spectra of 3ω,4ω, and 5ω pulses generated by cascaded four-wave mixing
are shown in figure 3. The transform-limited pulse widths are
estimated as 9, 7, and 6 fs for 3ω, 4ω, and 5ω, respectively.
The photoelectron velocity map imaging apparatus[17, 18] with a doubly-skimmed molecular beam sourceis employed with a pulsed gas valve [19]. Photoelectrons
generated by (1 + 1 ) resonantly enhanced two-photon
ionization of jet-cooled samples are accelerated in an electricfield and projected onto a dual microchannel plate (effective
area of 75 mm φ) backed by a phosphor screen (P46). The
linear polarization vectors of the VUV and deep UV pulses
are aligned parallel to each other and also set parallel to themicrochannel plate detector face. Photoelectron images arerecorded as a function of the delay time between deep UVand VUV pulses and analysed by the pBASEX method [20]to obtain time-dependent photoelectron kinetic energy andangular distributions.
The cross-correlation trace between 4ω and 5ω measured
using non-resonant (1 + 1 ) two-photon ionization of
Xe is shown in figure 4. The background signal (∼640)
originates from two-photon ionization by individual onecolour ionization processes. As shown in figure 3, the observed
trace is well expressed by a single Gaussian with a full widthat half maximum of 17 ± 2 fs (a solid line); which suggeststhat the individual pulses of 4ω and 5ω have pulse durationsof about 12 fs.
The ω + 2ω is not the only method for generation of
5ω. Zuo et al employed the 2ω + 3ω scheme to generate 4ω
and 5ω simultaneously [16, 21]. If only 5ω is necessary, one
can also employ the ω + 3ω scheme. With the latter, Ghotbi
et al demonstrated generation of 2.5 μJ pulse−1 radiation at
160 nm using noncollinear geometry for four-wave mixing[22]. Beutler et al have employed a tandem filamentation cellto compress ω and perform the ω + 3ω scheme to generate a
16.4 fs pulse at 160 nm [23].

Figure 2. Photograph of filamentation in Ne gas.

residual fundamental. The fundamental beam is focused into
the cell with another dielectric concave mirror (r = 2,000 mm).
A flat dichroic mirror is used to recombine the fundamental
and second harmonic beams. The relative polarization of two
beams is parallel to each other. The pulse energies of thefundamental and the second harmonic are 0.43 and 0.37 mJ,
respectively. When the ω and 2ω pulses overlap temporally andspatially, a bright filament (plasma column) with the length ofca. 120 mm is created (figure 2).
For obtaining VUV radiation from the filamentation cell,
one may use an optical window such as MgF2. Then, dispersion
caused by the output window must be compensated, forexample, by chirping one of the input pulses [16]; however, ittransfers only the even orders of spectral chirp to the fourwave mixing pulse, so that dispersion cannot be perfectlycompensated. Alternatively, we avoid material dispersion
simply by eliminating transmissive optics in the paths after
the four-wave mixing. A pinhole is employed, instead of an
output window, for the filamentation cell to transmit the deep
UV and VUV pulses generated by four-wave mixing. The
neon gas leaking through the pinhole is evacuated with adry pump (580 L min−1). As shown in figure 1(b), a narrow
channel (1.25 mm in diameter and 20 mm in length) and an
aperture (3 mm φ) are placed behind the pinhole to minimize
conductance and improve differential pumping. The pressureof neon gas in the gas cell is ∼3.7 × 102 Torr. The pressure inthis first differential pumping section is below 3.0 × 10−1 Torr.
The region between the channel and the aperture is evacuatedwith another dry pump (500 L min−1). The flow rate of neon
gas is 0.5 Torr · L s−1.
The laser pulses finally enter a high-vacuum optics
chamber that houses an optical delay stage and mirrors. A
UV-enhanced aluminium mirror with an aperture of 3 mmdiameter is used to spatially separate the central and peripheral
parts of the beam. The central part is transmitted through thisholed mirror and reflected five times with dielectric mirrors
for 5ω in order to attenuate other colours (ω, 2ω, 3ω and 4ω).
The peripheral part reflected by the holed mirror is used tosample 3ω or 4ω, using dichroic mirrors. The timing of the5ω pulse is varied using a vacuum-compatible translational
stage with 5 nm resolution. The VUV and deep UV pulses
are independently focused onto a molecular beam with two
Al concave mirrors (r = 1000 mm). The intersection angle

2.2. Photoelectron imaging of S2–S1 internal conversion inpyrazine

The S2(1B2u, π π ∗ )–S1(1B3u, nπ ∗ ) internal conversion ofpyrazine (C4H4N2, D2h) is one of the best-known examples
of ultrafast electronic deactivation via a conical intersection[24]. The topography of this conical intersection has been
extensively studied by ab initio molecular orbital calculations(see [25] and references therein). Although pyrazine has
24 normal modes, only a single mode, Q10a(b1g), mediates
S2–S1 coupling due to the selection rule. Furthermore,
only a few totally symmetric (ag) modes participate in
the short-time vibrational dynamics of this system. This
reduced dimensionality makes pyrazine a benchmark fortheoretical studies of ultrafast internal conversion via a conicalintersection. However, real-time observation of this process
was not possible owing to the lack of a suitable ultrafast laser
in the deep UV region.
3

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001(a)Review Article

(b)

(c)

Figure 3. Typical spectra (a) 3ω, (b) 4ω, and (c) 5ω. Reprinted with permission from [7]. © 2013 The Optical Society of America.

(a)

(b)

Figure 4. Cross-correlation trace between 4ω and 5ω pulses

measured by non-resonant two-photon ionization of an atomic beamof Xe.

Figure 5(a) shows the UV photoabsorption spectraof pyrazine (pyrazine-h4) and fully deuterated pyrazine(pyrazine-d4) vapour measured at room temperature. Overlaid
are the spectra of our pump (264 nm: blue) and probe (198 nm:red) pulses. The pump pulse overlaps with the S2–S0 band near
the origin, while the probe pulse overlaps (unfavourably) with
the S3–S0 band slightly. Figure 5(b) shows a schematic energy
diagram of our experiment. The sum of the photon energies ofthe pump (4.70 eV) and probe (6.26 eV) pulses is 10.96 eV,
which enables ionization to the three ion states of D0, D1, andD2 energetically.
The photoelectron kinetic energy and angular distributionin (1 + 1 ) photoionization is expressed as follows (the primemeans different colour):σ (t, E ){1 + β2 (t, E )P2 (cos θ )I(t, E, θ ) =4π(1)+ β4 (t, E )P4 (cos θ )}Figure 5. UV photoabsorption spectra of (a) S1, S2, and S3 ofpyrazine-h4 (orange solid line) and pyrazine-d4 (green dashed line)
at room temperature. The spectra of our pump (264 nm, 4.70 eV)
and probe (198 nm, 6.26 eV) pulses are also shown in blue andviolet. (b) Schematic energy diagram of pyrazine. Reprinted withpermission from [26]. © 2010 American Institute of Physics.

observables in (1 + 1 ) TRPEI (time-resolved photoelectron
imaging). Extraction of dynamical information from β 2(t, E)
and β 4(t, E) is the heart of TRPEI.
Figure 6 presents the experimental results of TRPEI of
pyrazine [25, 27, 28]. Figure 6(b) shows the total photoelectron
signal as a function of the pump–probe time delay. Since thespectra of our pump and probe pulses overlap the S2–S0 and
S3–S0 bands, respectively, the 264 nm pulse excites groundstate molecules to S2 and the 198 nm pulse ionizes them for apositive time delay, while for a negative time delay, the roles of
the 198 nm and 264 nm pulses are interchanged and molecules
are ionized from S3. The signal at a positive time delay
rapidly decays in less than 30 fs and exhibits a plateau; thiswhere t, E, θ , and are the pump–probe time delay, thephotoelectron kinetic energy and the electron ejection angle
from the laser polarization direction. Pn(x) are the nth order
Legendre polynomials. σ (t, E) represents a photoelectron
kinetic energy distribution (photoelectron spectrum). β 2(t, E)
and β 4(t, E) are called anisotropy parameters. The three scalarquantities of σ (t, E), β 2(t, E) and β 4(t, E) in equation (1) are the4

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article

(a)

(b)

(c)

(d)

(a)

(b)

Figure 7. Electronic configurations of D0 and S2. The leading
configurations of D0 and S2 are shown in (a) and (c), respectively. By
two-electron excitation, configurations (b) and (d) are obtained from
configurations (a) and (c), respectively. Arrows indicate the allowedtransition by one-photon ionization. Filled circles represent
electrons. Isolated electrons at the top of panels (a) and (b) represent
photoelectrons.

(c)figure 5(b), is a fingerprint of the electronic character. The
time–energy map clearly shows that there are three different
components, one at a negative time delay and two at a positive
time delay, which agrees with the analysis of σ (t, E). The
most distinctive feature is the sudden change in the colour
at ca. 30 fs, which is attributed to ultrafast S2 → S1 internalconversion. β 2(t, E) does not change after 30 fs, indicatingthat the (n, π ∗ ) electronic character remains; no restorationof the (π ,π ∗ ) character is identified. This lack of recurrenceis possibly related to the photoexcitation energy; we excited
pyrazine near the S2 origin. Consequently, if the vibrationalenergy flows into various modes in S1, the wave packet has nochance to return to the Franck–Condon region in S2.
Within the lifetime (22 fs) of the S2 state, a PKE > 0.8 eV
is created by D0 ← S2. However, this ionization process isforbidden for the main electron configurations of D0 andS2; therefore, the occurrence of this process indicates thatD0 and S2 consist of multiple electron configurations. The
D0 configurations that can be created by one-photon ionizationfrom S2 are those obtained by removing one electron from an
orbital (φ) of the S2 configuration, i.e.,

Figure 6. (a) Time-evolution of the photoelectron kinetic energy
distribution, σ (t, E). (b) Temporal profiles of the total photoelectron
signals in (1+1 ) TRPEI of pyrazine-h4. The observed data are well
explained by three components: single-exponential decay ofS2 (red), corresponding increase in S1 (blue) at a positive time delay,and single-exponential decay of S3 (green) at a negative time delay.
The fitting result is shown by the solid line. (c) Time-evolution ofphotoelectron angular anisotropy parameter β 2(t, E).

plateau has a finite lifetime of 22 ps for pyrazine-h4 [29, 30].
Furthermore, the plateau region exhibits oscillatory featuresdue to vibrational quantum beats. The Fourier transform of
the oscillation (t > 50 fs) exhibits a frequency component of
560 ± 40 cm−1, which agrees with the vibrational frequency
of Q6a in S1 (583 cm−1). In the negative time range, thesignal diminishes very rapidly within 100 fs (towards the −∞direction). The observed profile can thus be explained bythree components: the decay of optically excited S2, thecorresponding growth of S1 populated by internal conversion
from S2, and the decay of S3. By least-squares fitting, theS2 → S1 internal conversion time constants are estimated to be
23 ± 4 fs. The σ (t, E) shown in figure 6(a), does not exhibit any
marked change on S2 → S1 internal conversion. This is because
photoionization occurs predominantly as D0(n−1) ← S1(n,π ∗ )and D1(π −1) ← S2(π ,π ∗ ), and the energy gaps between D1 andD0 (0.88 eV) and between S2 and S1 (0.86 eV) are almost thesame.
Figure 6(c) shows a time–energy map of β 2(t, E). The
positive (blue–green) and negative (red) values correspond topreferential ejection of an electron parallel and perpendicular
to the probe laser polarization [see equation (1)]. The energy
dependence of β 2, a coloured stripe at each time delay inψ (S2 ) = ψ (D0 ) × φ,(2)

where (S2) and (D0) respectively denote the electron
configurations of S2 and D0. Because (D0) × φ should havethe same symmetry species as S2 [ (S2) = (D0) × (φ)],φ must be the b2u orbital as given by the direct product
Ag(D0) × B2u(S2). However, no b2u orbital exists among
the outer valence and π ∗ orbitals, which implies thatD0 ← S2 cannot be well described by typical valence complete
active space self-consistent field (CASSCF) wavefunctions. To
make the calculations tractable, we focused on configurations
that are doubly excited with respect to the main configuration[28]. Figure 7 shows examples of such configurations.
The configurations shown in figures 7(b) and (d) can beobtained by two-electron excitations from the D0 and S2 main
configurations shown in figures 7(a) and (c), respectively.
Ionization from the configuration in figure 7(d) to that in 7(a)5

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article(a)Figure 9. Photoelectron kinetic energy distribution observed forpyrazine using 264 nm pump and 159 nm probe pulses. Negative
delay times indicate that the probe pulse precedes the pump pulse.
The panel on the right shows the distribution integrated for the timedelay of 50–150 fs.

(b)being too low. Thus, we also performed TRPEI experiments
using VUV radiation from SCSS as a probe pulse [31].
Figure 8 compares the photoelectron spectrum measured using
the probe pulses of 161 nm radiation from SCSS and the
198 nm radiation from our filamentation four-wave mixing
light source in the laboratory [31]. The former distribution
exhibits a maximum in the region ca. 1.2 eV above D0, whichis consistent with the vibrational energy of ca. 0.9 eV in
S1. Since S1 is the (n,π ∗ ) state and D0 and D1 are n−1 andπ −1 states, the frozen-core approximation predicts ionization
occurs from S1 to D0, as discussed earlier. On the other hand,since SCSS uses SASE, the timing jitter between the SCSS
and a femtosecond laser is of the order of sub-picoseconds,
which did not enable us to observe S2–S1 ultrafast internalconversion in pyrazine in real time. Therefore, we generated
VUV radiation (159 nm) using filamentation four-wave mixing
and revisited this problem.
Figure 9 shows the time–energy map of the photoelectronenergy distribution observed using the filamentation lightsource. In the negative time range, three Rydberg states of
3s, 3py and 3pz exhibit sharp horizontal distributions and avalence state exhibits a distribution that diminishes the kinetic
energy rapidly and disappears within 100 fs. In the positive
time range, the photoionization from S2 and S1 are observed,
although the signal around t = 0 is rather congested due to boththe 264 nm pump and 159 nm pump signals. The photoelectron
kinetic energy distribution after the pump–probe delay of
100 fs is essentially the same as that obtained using
SCSS. More detailed accounts of these results are presented
elsewhere.

Figure 8. (a) PKED in He(I) photoelectron spectroscopy ofground-state pyrazine (black), 264 nm pump and 198 nm probe
experiment (red) and 260 nm pump and 161 nm probe (blue). (b)Schematic energy diagram of the ionization process. Insets show the
UV absorption spectrum of pyrazine vapour at room temperature
and a time-averaged spectrum of SCSS. Reprinted with permission
from [31]. © 2010 American Physical Society.

and from the configuration in figures 7(c) to 7(b) is possible.
Including these configurations, the first-order configurationinteraction calculations account for all one-electron excitations
from the complete active space of eight orbitals. From ourcalculations, we find the contributions to the spectral intensity[42] of 47% from 3b2u, 27% from 4b2u, and 26% from all
virtual b2u (jb2u, j  5) [28]. This result clearly demonstrates
that the electron correlation cannot be neglected for either
D0 or S2.
The σ (t, E) shown in figure 6(a) exhibits non-zerointensity down to 0 eV. This clearly demonstrates that
the Franck–Condon envelopes are not fully covered forphotoionization from S2 and S1 due to the probe photon energy

2.3. Photoelectron imaging of internal conversion in furan

Furan (C4H4O, C2v) exhibits a broad UV absorption spectrum
that has been ascribed to four electronic transitions to the1
A2(π ,3s), 1B2(π ,π ∗ ), 1A1(π ,π ∗ ), and 1B1(π ,3py) states, inwhich the transition to 1A2 is weakly allowed by vibronic
6

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article

0.4 eV than the maximum possible energy of 2.0 eV, whichis consistent with the estimated vibrational energy in S1, ca.
0.3–0.4 eV. The region B exhibits a broad σ (t, E) and low β 2,which indicates ionization from a valence state 1B2(π , π ∗ ).
The intensity maxima of σ (t, E) in region B are systematicallytime-delayed for lower energy. The lag time is ascribed tovibrational wave packet motion from the Franck–Condon
region to the molecular structure monitored with a particular
photoelectron kinetic energy. The results suggest that themolecules photoexcited to 1B2(π , π ∗ ) undergo large structuraldeformation within 50 fs, and that they do not undergo
efficient internal conversion to 1A2(π , 3s), contradicting withthe theoretical prediction previously made [33, 34].
Theoretical simulation of TRPEI of polyatomic molecules
is a highly challenging task. One difficulty arises from thefact that a polyatomic molecule has a number of vibrational
degrees of freedom, for which accurate calculations of thepotential energy surfaces and propagation of nuclear wave
packet are computationally highly demanding. Calculations
with reduced vibrational dimensionality are not desirable,
because the photoionization Franck–Condon factor has tobe taken into account for all vibrational degrees of freedom
even if ultrafast dynamics in the excited electronic state(s)occur within limited vibrational degrees of freedom. This isclear when a large geometrical change occurs between theneutral and cationic states. Another difficulty arises in thetheoretical description of ionization continua and calculationsof transition dipole moments for bound-free photoionization.
As our experimental study on pyrazine [25] has demonstrated
clearly, the photoelectron angular distribution can reveal anabrupt change of electronic character upon a non-adiabatic
transition, so that the theoretical model should be able
to simulate the photoelectron angular anisotropy. One of
the methods to obtain the photoionization transition dipole
moments is Schwinger variational calculations [35]. Arasaki
et al have performed such calculations on TRPEI of the excitedstate dynamics of NO2 [36].
The photophysics of furan has been previously studied
by multiconfigurational time-dependent Hartree wavepacket
calculations with the potential energy surfaces determined by
the ab initio equation-of-motion coupled cluster method [34].
The calculations predict that the 1B2(π , π ∗ ) state undergoes
ultrafast internal conversion to 1A2(π , 3s) within ∼25 fs
through a conical intersection, while the lifetime of 1A2(π , 3s)
is longer than 200 fs. The conical intersection with S0, however,
was not considered in these calculations. Another theoretical
study, using a combined density functional/multireference
configuration interaction method, suggested that molecules
excited to the 1B2(π , π ∗ ) state undergo a ring-opening
reaction via the 1B1(π , σ ∗ ) state [37]. We have simulated
the TRPEI of furan using molecular dynamics (MD) on
the fly in the frame of TDDFT and assuming constantphotoionization transition dipole moments to the D0 state[26]; MD on the fly is a method that calculates classicaltrajectories for all vibrational coordinates using the forces
given by TDDFT. The simulations have reproduced theexperimental photoelectron kinetic energy spectra; however,
the method did not enable calculations of the photoelectron

(a)

(b)

Figure 10. (a) Absorption spectrum (blue) of furan at room

temperature and theoretical spectrum (red) for S1(1A2(π , 3s)) andS2(1B2(π , π ∗ )) states at T = 300 K. The discrete absorption lines foreach member of the ensemble were convoluted with a Lorentzianfunction with a width of 0.1 eV and added together. The spectra of
our pump (6.2 eV, 200 nm) and probe (4.7 eV, 260 nm) pulses areshown as filled curves. (b) Equilibrium structure of furan in theneutral ground state with character of the S1(π , 3s) and S2(π , π ∗ )transitions. Reprinted with permission from [26]. © 2010 American
Institute of Physics.

coupling with 1B2. Figure 10 shows the absorption spectrum atroom temperature and the corresponding theoretical spectrum
calculated by time-dependent density functional theory [13].
The strong absorption feature at ∼6 eV is due to theS2 ← S0 transition, and the weak feature in the low energy part
(5.6–6.0 eV) corresponds to the S1 ← S0 transition. Anotherstrong transition of 1B1(π ,3py) ← S0 is at 6.45 eV and outsideof our pump spectrum.
The observed time profiles of photoion and photoelectron
signals are shown in figure 11(a). The least-squares fitting
assuming a single exponential function (green solid line infigure 11(a)) provides the lifetime of the excited state as
46 fs; the single exponential decay, however, does not provide
an adequate fit of the time profile. For comparison, a time
profile extracted for the specific kinetic energy of 1.6 eV iswell reproduced by a single exponential function, as shownin a solid line in figure 11(b). The signal in figure 11(b)appears immediately at the time origin, indicating that thisstate is directly photoexcited from S0: the lifetime of this stateis 29 fs.
The experimental time–energy maps of σ (t, E) andβ 2(t, E) are respectively shown in figures 12(b) and 13(b)[32]. Each map can be separated into regions of E >1.5 eV(region A) and 0.0–1.5 eV (region B). The former exhibitshigh β 2 values (∼0.8) that are typical of photoionization froma 3s Rydberg state. The kinetic energy of 1.6 eV is smaller by7

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

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(a)

(b)

Figure 11. (a) Temporal profiles of total photoelectron (solid circles) and photoion (dotted line) signal in (1 + 1 ) TRPEI of furan. The resultof least-squares fitting with a single exponential decay [exp(−t/τ )] convoluted with our apparatus function (Gaussian with 22 fs FWHM) is
also shown as a solid line (τ = 46.3 fs). (b) Temporal profile of photoelectron intensity at a photoelectron kinetic energy of 1.6 eV. The
result of least-square fitting with a single exponential decay convoluted with the apparatus function is shown as a solid line (τ = 29.0 fs).
Reprinted with permission from [26]. © 2010 American Institute of Physics.
(a)

(b)

Figure 12. (a) Calculated photoelectron kinetic energy (PKE) distribution σ (t, E) for 198 nm photoexcitation and 264 nm photoionization offuran. (b) Experimentally observed σ (t, E). The vertical dotted line is at a delay time of 10 fs, where the temporal peaks of high-energy
components appear. The high and low energy components, separated by horizontal lines, were denoted by A and B, respectively. Reprinted
with permission from [32]. © 2013 American Institute of Physics.

(a)

(b)

Figure 13. (a) Calculated values of the time-dependent photoelectron anisotropy parameter β 2(t, E) for furan. The high and low energy
components, separated by horizontal lines, were denoted by A and B, respectively. (b) β 2(t, E) extracted from observed photoelectron
images of furan. Reprinted with permission from [32]. © 2013 American Institute of Physics.

angular anisotropies. Therefore, Mitric and coworkers have
improved the description of the ionization process using theDyson orbital for the ionized orbital and atomic partial waves
in a pure Coulombic potential for the photoelectron wave
function [32]. The Dyson orbital is a single electron wave
function defined as the overlap between the neutral electronic
state with N electrons and the cationic state with N−1electrons, and it facilitates a simple and reasonably accurate
description of the photoionization step. Approximation ofa photoelectron wavefunction using partial waves in a pure
Coulombic potential ignores the dynamical phase shifts of thepartial waves and shape resonances. The accuracies of theseapproximations need to be tested against experimental resultson various systems.
Figure 12 compares (a) the theoretical simulation by
Mitric and coworkers and (b) the experimental result [32].
The theoretical simulation well reproduces formation of the
3s Rydberg state in the energy region indicated as A and rapid
motion of the wave packet across region B within 50 fs. A
more impressive agreement with the experiment is the time–energy map of anisotropy parameter shown in figure 13. Notethat the absolute magnitudes of the anisotropy parameters
are different between the theoretical and experimental results.
However, the general trends are in good agreement. First of8

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article

all, high anisotropy observed for the 3s Rydberg state in region
A is well reproduced in the calculation. Lower anisotropies inregion B are also found in both the calculation and experiment.
The high anisotropy experimentally observed at around 0.2–
0.3 eV is due to ionization to the D1 state of furan; however,when a major component of D0–S2 produces photoelectrons
in the same energy region at around a time delay of 20–
30 fs, it dominates and reduces the anisotropy suddenly. The
calculation captures this sudden drop of the photoelectron
anisotropy. Thus, comparison with our experiment reveals
that calculations based on the crude approximations using theDyson orbital and atomic partial waves in Coulombic potential
still provide useful theoretical support to experiments.

Figure 14. Photoabsorption spectrum of CS2 showing sharp
vibrational progressions (reprinted with permission from [45].
© 1983 American Institute of Physics) and the broad spectrum of
our pump pulse.

2.4. Photoelectron imaging of ultrafast dynamics in CS2

CS2 is linear in the electronic ground state (1 g+), while
photoexcitation in the wavelength region of 192–208 nm
promotes a molecule to 1B2(1 u+) with a quasi-linear structure.
This photoexcitation induces symmetric stretching (ν 1 =392 cm−1) and bending (ν 2 = 426 cm−1) vibrations. At 198 nm,
the molecule is above the barrier for linearity, so that a large
amplitude vibration occurs in the bending mode between thelinear and bent geometries. Although the 1B2(1 u+) state isbound in the linear geometry, it undergoes avoided crossings
with the repulsive 1B2(1g) state at large bending angles,
so that the molecule predissociates into CS(1 +) + S(1D)and CS(1 +) + S(3P). The photodissociation dynamics of
CS2 have been studied by a number of researchers, while
ultrafast spectroscopy has been limited [38–44].
Farmanara et al studied the ultrafast excited state
dynamics of CS2 in the 1B2(1 u+) state using a 201.4 nm
pump pulse and a 268 nm probe pulse in 1999; the pulse
duration was ca. 130 fs [38]. The observed transient ion signal
was approximated as a single exponential decay associated bya vibrational quantum beat. The time-resolved photoelectron
spectra of CS2 was observed in 2006 by Townsend et al using a
201.3 nm pump and a 268 nm probe pulses [40]. Essentially thesame yet more detailed spectra was also reported by Bisgaard
et al in 2009; furthermore, Bisgaard et al aligned CS2 by
non-resonant rotational excitation using an 805 nm pulse prior
to performing pump–probe photoelectron spectroscopy andmeasured the photoelectron angular distribution for the aligned
ensemble of molecules [41]. Hocket et al have presented
detailed accounts on these time-dependent photoelectron
angular distributions [43]. Fuji et al have applied sub-20 fs
deep UV pulses (198 and 264 nm) generated by filamentation
four-wave mixing to the excited state dynamics of CS2 in 2011;
the cross-correlation was 22 fs [44]. With a considerably higher
time resolution, the transient photoelectron spectra exhibitedvery clear wave packet motion in the 1B2(1 u+) state. All ofthese previous studies [38–44] employed the third harmonicof the Ti:sapphire laser as the probe pulse; however, the probe
photon energy was insufficient for observing the entire wave
packet dynamics on the excited state potential energy surfaces.
Horio et al revisited the dynamics in the 1B2(1 u+) stateusing sub-20 fs 198 nm pump and 159 nm probe pulses
described in section 2 [7]. As shown in figure 14, the broad

198 nm pump pulse covers almost entire 1B2(1 u+)–1A1(1 g+)
photoabsorption spectrum of CS2 and creates a spatiallyconfined initial wave packet. Figure 15 compares the two time–energy maps of photoelectron spectra measured using (b) the
198 nm pump and 264 nm probe pulses and (c) the 198 nm
pump and 159 nm probe pulses. The latter exhibits very clear
oscillatory motions of vibrational wave packet. The signal at
4 eV corresponds to photoionization from the linear geometryof CS2 while the signal at around 1.3 eV is from the turning
point at the bent structure. Observation of such clear wave
packet dynamics was not possible with longer pulse durations
and longer probe wavelength employed in previous studies. As
schematically shown in figure 15(a), the CS2+ cation is linear,so that high photon energy is required for photoionization fromthe bent structure to vibrationally excited states of the cation.
3. Subpicosecond time-resolved x-ray absorption
spectroscopy using a hard x-ray free electron laser
The orbital energies of inner-shell electrons largely varywith the atomic numbers, and their energies further
exhibit ‘chemical shifts’ depending on the chemical bonds
formed by the atoms. X-ray photoelectron spectroscopy
enables measurements of these chemical shifts, so that
x-ray photoelectron spectroscopy is also termed electron
spectroscopy for chemical analysis [46, 47]. Another method
to measure the chemical shift is x-ray absorption spectroscopy,
in which the x-ray absorption intensity steeply increases
when photon energy exceeds the electron binding energy.
Furthermore, the absorption spectrum exhibits structures in
the post-ionization region, which are useful for extracting
geometrical structure around the electron-emitting atom. The
spectral feature within ca. 50 eV from the edge, called
XANES (x-ray absorption near edge structure), is due to shaperesonance, transient electron trapping by a molecule. The
structure far above the ionization threshold is called EXAFS(extended x-ray absorption fine structure), which is caused
by quantum mechanical interference between an outgoing
photoelectron wave and the scattered waves from adjacentatoms. From the oscillatory features in EXAFS, interatomic
distances between the electron-emitting atom and adjacent9

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001(a)Review Article

(b)

(c)

Figure 15. (a) Schematic potential energy diagram of CS2. Two-dimensional (2D) map of photoelectron kinetic energy (PKE) distributions
as a function of the pump–probe delay time using (b) a 3ω probe pulse and (c) a 5ω probe pulse.

Figure 16. Experimental setup for the dual-beam dispersive detection method. Spatial overlap of the sample liquid beam, pump laser andx-ray is depicted in the upper right inset. Temporal sequence of 400 nm pump and x-ray probe pulses is shown in the upper left inset.
Reprinted with permission from [15]. © 2014 The Optical Society of America.

atoms can be determined. With the element-specificity
and structural information, time-resolved x-ray absorption
spectroscopy (TRXAS) serves as a useful experimental
method to probe the electronic and structural dynamics ofmaterials. The ability of XAS to probe the local structureis, in some sense, similar to resonance Raman spectroscopy
employed for studying local structures of macromolecules.
Readers interested in general principle of TRXAS, particularly
with liquid targets, can refer to excellent review articles
published previously [48–52].
When synchrotron radiation is employed, the time
resolution of TRXAS is tens of picoseconds. The time
resolution can be improved by using a time-slicing technique,which extracts a femtosecond x-ray pulse using interactionof a femtosecond visible laser pulse with an electron
bunch in a storage ring [53, 54]. However, the time-slicing

technique inevitably sacrifices photon flux and produces only
10–100 photons/pulse. XFELs offer considerably higher
photon fluxes of more than 1010 photons/pulse and are opening
a new avenue for TRXAS. XFEL-based TRXAS has alreadybeen implemented at LCLS and SACLA. At LCLS, TRXAS
was performed by fluorescence detection, in which x-ray
fluorescence from the target was monitored while scanning
the x-ray photon energy [55]. At SACLA, direct absorption
spectroscopy was performed using a broadband x-ray radiationand x-ray polychromator [15, 56]. The advantage of XFELbased TRXAS is its high time-resolution; note, however, thatthe actual time resolution is limited to several hundred fs to
1 ps owing to timing jitter of the XFEL, even if the x-ray
pulse duration is as short as tens of fs. The disadvantage of
XFEL-based TRXAS is a low duty cycle, which is restrictedby the repetition rate of XFEL, currently 120 Hz at LCLS and
10

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

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30 Hz at SACLA. These repetition rates are contrasted withkHz (fs pulses) to MHz (ps pulses) repetition rates of TRXAS
at synchrotron radiation facilities, which are limited by therepetition rates of synchronous lasers [57, 58]. Because of ahigh-repetition rate and stability, TRXAS using synchrotron
radiation can be applied to dilute solutions at concentrationlevels down to mM; XFEL-based TRXAS requires tens of
mM. The XFEL-based TRXAS also has the limitation of a
fixed beam time, because the XFEL is a linear accelerator andonly a few experiments can be performed at one time.
At LCLS, Lemke et al have studied photoinduced
dynamics of spin crossover in the iron (II) tris(2,2 bipyridine)
complex in water using a 400 nm pulse and hard x-ray radiation(ca. 7.1 keV at the K-edge of Fe) [55]. The timing jitter between
the pump and probe pulses was estimated to be 160 fs fortime scans while between 300 and 500 fs in spectral scans.
The TRXAS experiment at SACLA has been performed undersimilar conditions [15].
Figure 16 shows the experimental setup employed at
SACLA [15]. The x-ray radiation from SACLA is split using
a transmission grating. The zero-order (undiffracted) x-ray
beam is blocked, and the +1(upper) and −1(lower) order
x-rays are employed as the signal and reference beams,
respectively. Each of these beams has a pulse energy of
1.4 μJ (1.2 × 109 photon/pulse at 7.12 keV). Two beams
are focused using a single elliptical mirror, in which only
the signal beam intersects with a sample liquid jet at the
focal point while the reference beam does not. The spot sizeof the signal beam on the sample is 250 μm (vertical) by
25 μm (horizontal). The polychromator consists of an ultraprecisely figured elliptical mirror, a diffraction grating of a flat
silicon (1 1 1) crystal, and a multi-port charge-coupled device(MPCCD) detector [20]. The signal and reference spectra arerecorded simultaneously with the MPCCD for each XFEL shot
to extract the absorption spectrum. The MPCCD has a pixel
size of 50 × 50 μm2, an imaging area of 25.6 × 51.2 mm2,
and a quantum efficiency of ca. 0.6 at 7 keV. The spectral rangeof the spectrometer is 67 eV, which is wider than the XFEL
bandwidth. The spectral resolution of the polychromator is ca.
1 eV. The photon numbers incident to each pixel of MPCCD
is ca. 7 × 102. A single x-ray photon creates 2,000 electron–
hole pairs while the system noise is about 300; therefore, the
MPCCD enables single photon counting. The 400 nm lightis the second harmonic of a Ti:sapphire laser with a homemade double-pass power amplifier added to a commercial
regenerative amplifier. The 400 nm pump pulse has a time
duration of 100 fs (fwhm), pulse energy of 1.1 mJ, and the spot
size is 400 μm (vertical) by 100 μm (horizontal) which is larger
than the spot size of the x-ray probe pulse at the sample. The
fluence of 400 nm laser is 3.5 J cm−2 on the sample. The 400 nm
pump and x-ray probe beams are crossed at the sample with asmall angle of less than 10◦ . The cross-correlation including
the timing jitter is about 200 fs; while the time zero graduallydrifts less than 1 ps for integration times of many hours. The
labelling of individual pulses and sorting of the signals foreach pump–probe delay will improve the time-resolution. The
400 nm pulse illuminates the sample synchronously with every
other x-ray pulse. Therefore, the transient absorption signal is

Figure 17. The minimum detectable absorbance using single-beam
detection (black squares) and dual-beam detection (red circles).

extracted as the difference between the absorption spectra foreven and odd-numbered x-ray pulses. Owing to the stochastic
nature of the SASE-XFEL, the single-shot spectrum of XFEL
has a spiky structure and the spectrum also fluctuates on a shotto-shot basis. The difference spectrum extracted by the dual
beam method eliminates the spiky structure and integration
over 500 shots smooth out the spectral fluctuation. Figure 17
shows the minimum absorbance detectable using only a single
reference beam (black square) or dual beams (red circle) in thepump–probe experiment plotted as a function of the numberof pump–probe pulse pairs. With the single beam method, theminimum detectable absorbance does not reach 1% even after
6000 pulse pairs, while the dual beam method achieves well
below 1% at 1000 pulse pairs. Thus, it is effective to use thedual beam method to detect a small transient absorption signal.
Femtosecond TRXAS was performed for aqueous 0.5 M
ammonium iron(III) oxalate trihydrate solution. Rentzepis andcoworkers [59, 60] have previously studied photochemistryof a ferrioxalate complex using TRXAS with a laser-plasma
x-ray source; however, the detailed dynamics have not been
understood yet. We employed this system for the firstfeasibility test of our TRXAS using SACLA. The sample
was discharged into air from a fused silica capillary with a
100 μm inner diameter and at a flow rate of 5 mL min−1.
The liquid beam was a cylindrical shape, and its speed was
10.6 m s−1. The sample concentration was selected to makethe optical density for x-ray radiation reasonably high; themolar extinction coefficient ε at the K-edge of iron (7.1 keV)
is 22.8 cm−1 M−1 and the absorbance for aqueous 0.5 M
solution is about 0.1. For observing the pump–probe signal,
we need to photoexcite a large fraction of molecules in theobservation region with the pump pulse. The number of ironcomplexes in the volume illuminated by x-ray is estimatedas 1.5 × 1014. Since the molar extinction coefficient at
400 nm is 160 cm−1 M−1 [13], photon numbers of more than
8.8 × 1013 are required for pumping half of these complexes to11

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(a)

(b)

Figure 18. (a) Time-resolved difference x-ray absorption spectra of aqueous 0.5 M ammonium iron(III) oxalate trihydrate solution.

(b) Temporal dependence of the absorbance change at 7.120 ± 0.004 keV in the difference absorption spectra. The instrumental response
function is shown in the dotted line, and the solid blue curve is least-squares fitting assuming a single exponential rise. Reprinted withpermission from [15]. © 2014 The Optical Society of America.
(a)

(b)

Figure 19. (a) Five different XFEL spectra employed to measure the transient absorption spectra for 7.10–7.26 keV. Each spectrum is theaverage over 20 000 shots. (b) Time-resolved difference absorption spectra. Each spectrum is constructed from five spectra of different
energy regions. Reprinted with permission from [15]. © 2014 The Optical Society of America.

the excited state. In terms of laser pulse energies this is 44 μJ
pulse−1. Since the pump laser spot size is 6.4 times larger
than the x-ray beam, the pump pulse energy should be at least
280 μJ pulse−1. Thus, we employed a rather intense pumppulse (1.1 mJ). A fresh sample solution kept in a container
covered with aluminium foil was used for measurements;
the sample solution was not circulated to avoid buildup of
the concentration of photodissociated products. The liquidflow rate and hydrodynamic stabilities were continuously
monitored using a high performance liquid chromatography
pump and a CCD camera, respectively. Entire experiments
were performed at room temperature and under atmosphericpressure.
Figure 18(a) shows the difference x-ray absorption spectraof the [Fe(C2O4)3]3- complex around the K-edge of the Fe
atom measured using the multiplex scheme at several pump–probe time delays. A positive absorbance change indicates anincreased absorption by 400 nm photoexcitation. The peak
position appearing at 7.12 eV is lower than the K-edge ofthe steady-state spectrum of the molecule. The shape ofthe difference spectra does not vary with the time delay.
Figure 18(b) shows the temporal dependence of the absorbancechange at 7.120 ± 0.004 keV. Assuming an instrumental
response time of 200 fs expected from timing jitter of the
x-ray pulse and the duration of the 400 nm pulse, the leastsquares fitting of the experimental data provides a rise time of
260 ± 50 fs as shown in solid line.
Figures 19(a) and (b) present the x-ray pulse anddifference absorption spectra for wider energy regions,
respectively. We employed five different central photon
energies, as shown in different colours in figure 19(a),by changing the undulator setting to observe the energy
12J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article

region of 7.10–7.26 keV. The difference spectra merged fromfive spectra taken for different energy regions are shownin figure 19(b) at six time delays. The spectral profile
is essentially the same even at a time delay of 100 ps.
Our result indicates that the transient species has a rather
similar geometrical structure with the ground state complex
and its lifetime is longer than 100 ps. With the limited
experimental evidences from the first TRXAS using SACLA,
the assignment of this transient species has not been made.
Further information such as transient infrared absorption
spectra, the lifetime measurements and kinetic analysis will beof assistance for elucidating its chemical nature. However, theresult clearly demonstrates impressive performance of ultrafast
TRXAS using SACLA. The largest absorbance change seenin figure 19(b) is 0.02, whereas the rms of the fluctuationin absorbance change is 0.002. The absorbance change of0.02 corresponds to variation of the arriving x-ray photon
numbers by 35 photons/pulse, so that the fluctuation of 0.002
is equivalent to 3.5 photons. Note that the system noise perenergy bin (10 pixels of MPCCD) is about 3.5 × 103 electrons,corresponding to 1.75 photons. Thus, the system noise of thedetector is an important factor for the minimal detection limit
using this method.

free electron laser is technically and financially challenging;
however, it is underway in Europe. Steering of kHz electron
beams into different beam lines will reduce the drawback of
the current free electron laser facilities by enabling several
experiments performed at the same time. The energy recovery
linac is one of other possibilities for future x-ray light sources.
Observation of pre-edge absorption features and the extended
x-ray absorption fine structure requires high sensitivity andstability of the spectrometer, especially when high timeresolution is pursued.
Both TRPES and TRXAS provide limited information on
nuclear dynamics in polyatomic molecules, which occur with
3 N-6 degrees of freedom (nonlinear molecules). Furthermore,
ultrafast electronic dynamics in solution undergo concurrently
with intra and intermolecular vibrational relaxation, so that the
spectrum of the same electronic state can change as a functionof time. Spectral analysis including vibrational cooling is quite
challenging. Mixed quantum/classical molecular dynamics(QM/MM) simulations will assist interpretation of suchcomplex experimental results.
Each of the advanced light sources based on a tabletop laser, a linear accelerator and a storage ring has different
advantages, and it is effective to make the best combinationof experimental measurements using different light sources tosolve a complex problem.

4. Summary and outlook

Acknowledgments

For elucidating chemical reaction mechanisms of polyatomic
molecules, it is essential to understand electronic dynamics,
including non-adiabatic transitions, which induce nuclear
dynamics in a molecule. Vacuum ultraviolet radiation
generated by filamentation four-wave mixing or high harmonic
generation is useful for observation of valence electronsin combination with photoelectron spectroscopy. When theprobe photon energy exceeds the electron binding energy ofa molecule, all energetically possible electronic deactivation
processes can be observed including internal conversion
down to the ground state. On the other hand, such highenergy probe photons will directly ionize the ground state
molecules, so that detection of the pump–probe signal becomesdifficult. This is also the case in x-ray absorption spectroscopy.
X-ray radiation is indispensable for probing inner-valence andinner-shell electrons and detecting the chemical shifts of theirbinding energies and the changes of post-ionization spectralfeatures; however, the ground state molecules dominate thex-ray absorption, so that the absorption spectra of photoexcitedspecies must be extracted from the difference spectrum(with and without the pump pulse). This usually requires
independent evaluation of the excitation efficiency using
the pump pulse. The pump–probe spectroscopy using shortwavelength radiation often requires complementary basic
information from the transient absorption or photoelectron
spectroscopies performed with visible and ultraviolet radiationin the laboratories.
A stable light source with a high-repetition rate will
be advantageous for spectroscopic purposes, especially ofdense targets such as liquids, even if the pulse energies arelimited. From this viewpoint, light sources with repetition
rates of 1 kHz or higher are attractive. Construction of a kHz

I express my gratitude to my group members, especially YoshiIchi Suzuki, Takuya Horio, Zuo Peng, Roman Spesyvtsev andYoshihiro Ogi for their essential contribution to the studies
described in this article. I am also grateful to Vlasta BonacicKoutechy and Roland Mitric for theoretical supports for
TRPEI, and Yuki Obara, Kazuhiko Misawa, Tetsuo Katayama
and Makina Yabashi and all members at SACLA for the joint
project on TRXAS.
References[1] Agostini P and DiMauro L F 2004 Rep. Prog. Phys. 67 1563
[2] Niikura H and Corkum P B 2007 Adv. At. Mol. Opt. Phys.
54 511[3] Krausz F and Ivanov M 2009 Rev. Mod. Phys. 81 163[4] Takahashi E J, Lan P, Mucke O D, Nabekawa Y
and Midorikawa K 2013 Nature Commun. 4 2691
[5] Fuji T, Horio T and Suzuki T 2007 Opt. Lett. 32 2481
[6] Fuji T, Suzuki T, Serebryannikov E E and Zheltikov A 2009
Phys. Rev. A 80 063822[7] Horio T, Spesyvtsev R and Suzuki T 2013 Opt. Express
21 22423[8] Chin S L 2010 Femtosecond Laser Filamentation (New York:
Springer)[9] Ackermann W et al 2007 Nature Photon. 1 336[10] Emma P et al 2010 Nature Photon. 4 641[11] Shintake T et al 2008 Nature Photon. 2 555[12] Ishikawa T et al 2012 Nature Photon. 6 540[13] Hara T et al 2013 Phys. Rev. Spec. Top.- Accel. Beams
16 080701[14] Yabashi M et al 2013 J. Phys. B: At. Mol. Opt. Phys.
46 164001[15] Obara Y et al 2014 Opt. Express 22 1105
[16] Zuo P, Fuji T and Suzuki T 2010 Opt. Express 18 16183
13

J. Phys. B: At. Mol. Opt. Phys. 47 (2014) 124001

Review Article[39] Hertel I V and Radloff W 2006 Rep. Prog. Phys. 69 1897
[40] Townsend D, Satzger H, Ejdrup T, Lee A M D, Stapelfeldt H
and Stolow A 2006 J. Chem. Phys. 125 234302[41] Bisgaard C Z, Clarkin O J, Wu G R, Lee A M D, Gessner O,
Hayden C C and Stolow A 2009 Science 323 1464
[42] Hockett F D, Wallace K D, Schmieder A H, Caruthers S D,
Pham C T N, Wickline S A and Lanza G M 2011 IEEE
Trans. Med. Imaging 30 22[43] Hockett P, Bisgaard C Z, Clarkin O J and Stolow A 2011
Nature Phys. 7 612[44] Fuji T, Suzuki Y I, Horio T and Suzuki T 2011 Chem.-An
Asian J. 6 3028
[45] Hemley R J, Leopold D G, Roebber J L and Vaida V 1983
J. Chem. Phys. 79 5219
[46] Hufner S 2003 Photoelectron Spectroscopy: Principles andApplications (Berlin: Springer)[47] Barr T L 1994 Modern ESCA: the Principles and Practice of
X-Ray Photoelectron Spectroscopy (Boca Raton, FL: CRC
Press)[48] Chen L X 2005 Annu. Rev. Phys. Chem. 56 221[49] Bressler C and Chergui M 2010 Annu. Rev. Phys. Chem.
61 263[50] Chergui M 2010 Acta Crystallogr. A 66 229[51] Chen L X and Zhang X 2013 J. Phys. Chem. Lett. 4 4000
[52] Penfold T J, Milne C J and Chergui M 2013 Advances in
Chemical Physics vol 153 ed S A Rice and A R Dinner(New York: Wiley)[53] Schoenlein R W, Chattopadhyay S, Chong H H W,
Glover T E, Heimann P A, Shank C V, Zholents A A
and Zolotorev M S 2000 Science 287 2237
[54] Beaud P et al 2007 Phys. Rev. Lett. 99 174801[55] Lemke H T et al 2013 J. Phys. Chem. A 117 735[56] Katayama T et al 2013 Appl. Phys. Lett. 103 131105[57] Lima F A et al 2011 Rev. Sci. Instrum. 82 063111[58] Haldrup K et al 2012 J. Phys. Chem. A 116 9878
[59] Chen J, Zhang H, Tomov I V, Wolfsherg M, Ding X L
and Rentzepis P M 2007 J. Phys. Chem. A 111 9326
[60] Chen W K, Chen J and Rentzepis P M 2013 J. Phys. Chem. B
117 4332[17] Chandler D W and Houston P L 1987 J. Chem. Phys. 87 1445
[18] Eppink A T J B and Parker D H 1997 Rev. Sci. Instrum.
68 3477[19] Suzuki T 2012 Int. Rev. Phys. Chem. 31 265[20] Garcia G A, Nahon L and Powis I 2004 Rev. Sci. Instrum.
75 4989[21] Zuo P, Fuji T, Horio T, Adachi S and Suzuki T 2012 Appl.
Phys. B 108 815[22] Ghotbi M, Beutler M and Noack F 2010 Opt. Lett. 35 3492
[23] Beutler M, Ghotbi M and Noack F 2011 Opt. Lett. 36 3726
[24] Schneider R and Domcke W 1988 Chem. Phys. Lett.
150 235[25] Suzuki Y I, Fuji T, Horio T and Suzuki T 2010 J. Chem. Phys.
132 174302[26] Fuji T, Suzuki Y I, Horio T, Suzuki T, Mitric R, Werner U
and Bonacic-Koutecky V 2010 J. Chem. Phys. 133 234303[27] Horio T, Fuji T, Suzuki Y I and Suzuki T 2009 J. Am. Chem.
Soc. 131 10392[28] Suzuki Y-I and Suzuki T 2012 J. Chem. Phys. 137 194314[29] Wang L, Kohguchi H and Suzuki T 1999 Faraday Discuss.
113 37[30] Stert V, Farmanara P and Radloff W 2000 J. Chem. Phys.
112 4460[31] Liu S Y et al 2010 Phys. Rev. A 81 031403[32] Humeniuk A, Wohlgemuth M, Suzuki T and Mitric R 2013
J. Chem. Phys. 139 134104[33] Gromov E V, Trofimov A B, Vitkovskaya N M, Schirmer J
and Koppel H 2003 J. Chem. Phys. 119 737[34] Gromov E V, Trofimov A B, Vitkovskaya N M, Koppel H,
Schirmer J, Meyer H D and Cederbaum L S 2004 J. Chem.
Phys. 121 4585
[35] Lucchese R R, Takatsuka K and Mckoy V 1986 Phys. Rep.
131 147[36] Arasaki Y, Takatsuka K, Wang K and McKoy V 2010
J. Chem. Phys. 132 124307[37] Gavrilov N, Salzmann S and Marian C M 2008 Chem. Phys.
349 269[38] Farmanara P, Stert V and Radloff W 1999 J. Chem. Phys.
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