Letter

pubs.acs.org/JPCL

First-Principles Calculations of the Energy and Width of the 2Au

Shape Resonance in pBenzoquinone: A Gateway State for Electron
Transfer
Alexander A. Kunitsa and Ksenia B. Bravaya*
Department of Chemistry, Boston University, Boston, Massachusetts 02215, United States
*
S Supporting Information

ABSTRACT: Quinones are versatile biological electron acceptors and mobile electron carriers
in redox processes. We present the rst ab initio calculations of the width of the 2Au shape
resonance in the para-benzoquinone anion, the simplest member of the quinone family. This
resonance state located at 2.5 eV above the ground state of the anion is believed to be a gateway
state for electron attachment in redox processes involving quinones. We employ the equation-
of-motion coupled-cluster method for electron anity augmented by a complex-absorbing
potential (CAP-EOM-EA-CCSD) to calculate the resonance position and width. The calculated width, 0.013 eV, is in excellent
agreement with the width of the resonant peak in the photodetachment spectrum, thus supporting the assignment of the band to
resonance excitation to the autodetaching 2Au state. The methodological aspects of CAP-EOM-EA-CCSD calculations of
resonances positions and widths in medium-sized molecules, such as basis set and CAP box size eects, are also discussed.

Q uinones are common members of electron-transfer

chains in biological systems.14 The most prominent
examples are ubiquinones and plastoquinones. Ubiquionones
serve as mobile intramembrane electron shuttles, transferring
electrons between the protein complexes of the mitochondria
respiratory chain.5 Plastoquinones act as terminal electron
acceptors in type II photosynthetic reaction centers.3,4 Owing
to their eciency in biological systems, quinones and quinone-
like compounds, for example, catechol-containing polydop-
amine, have been utilized in biomimetic photosynthetic
devices.6,7 Quinones paramount role in biological electron
transfer and potential technological applications stimulated
theoretical814 and experimental studies11,12,1518 of electronic
structure of model quinone compounds in dierent redox
states. The simplest and the most well characterized quinone is
para-benzoquinone (pBQ).
Electron attachment to neutral pBQ is exothermic, with an Figure 1. Photodetachment spectrum of pBQ.19 Vertical and
adiabatic electron attachment (AEA) energy of 1.860 eV 5 adiabatic excitation energies to 2Au and 2B3u states, calculated at the
meV as determined by photodetachment photoelectron XMCQDPT2/daug-cc-pVTZ level of theory (see the text for details),
studies19 of jet-cooled pBQ anions. The ground state of the are shown as solid and dotted bars, respectively. The vertical excitation
anion has D2h equilibrium geometry and is formed by electron energy to the 2B3u state is 2.91 eV. Adiabatic excitation energies
attachment to the lowest molecular orbital (MO), b2g (see include zero-point energy (ZPE) correction computed with CASSCF
Figure 1). Excited states are generated by promoting an (17/12)/6-311++G(2d,p) harmonic frequencies calculated for the
electron from one of the doubly occupied orbitals to the singly geometries optimized at the same level of theory (see Supporting
Information (SI), Figure S1).
occupied (SOMO) orbital ( or n excitations) or by
promoting an electron from the SOMO to higher-lying MOs.
Previous theoretical studies813 consistently identify two bright and width of the 2Au resonance. Note that although the two
states in the manifold of the low-lying excited states of the bright states are singly excited with respect to the ground state
anion, 2Au and 2B3u, which are derived from the b2g au and of the anion, their decay mechanism is dierent. Electron
b3u b2g one-electron excitations, respectively (Figure 1). detachment forming a neutral closed-shell (1Ag) target is a one-
Importantly, all excited states of pBQ anion (pBQ) are
vertically unbound and lie in the electron-detachment Received: January 30, 2015
continuum; thus, they are autodetachment resonances.813,20 Accepted: March 3, 2015
In this Letter, we focus on the characterization of the position Published: March 3, 2015

2015 American Chemical Society 1053 DOI: 10.1021/acs.jpclett.5b00207

J. Phys. Chem. Lett. 2015, 6, 10531058
The Journal of Physical Chemistry Letters
electron transition from the 2Au state, whereas the decay of 2B3u
is a two-electron processes. Thus, 2Au and 2B3u can be classied
as shape and Feshbach resonances, respectively. The latter are
expected to have longer lifetimes owing to the two-particle
character of the decay, which is driven by electron
correlation.21,22
Despite the large positive electron anity, electron attach-
ment to neutral pBQ proceeds more eciently via excited
electronic states of the anion. Unusual solvent, temperature,
and pressure dependence of the electron attachment rates to
benzoquinone2426 have been explained by an inverted Marcus
regime for the direct electron attachment to the ground state,
leading to a large activation energy and ecient electron
capture via excited states of the anion and their further
relaxation to the ground state. Hence, the positions and
lifetimes of these metastable states are of primary importance
for understanding the electron-transfer processes in quinones.
Electron-detachment resonances were accurately character-
ized by photodetachment and resonant photodetachment
photoelectron spectroscopy of the jet-cooled pBQ anions.19 A
pBQ photodetachment spectrum that represents the depend-
ence of the total yield of the ejected electrons on the excitation
energy is shown in Figure 1. The intensity in the photodetach-
ment spectrum corresponds to the collective yield of
photoelectrons with all possible kinetic energy values. The
intensity, in general, rises monotonously with photon energy
above the lowest detachment energy threshold in the case of
direct detachment into the continuum.19,27,28 Nonmonotonous
features are associated with strong resonant absorption into
metastable excited states of the anion followed by auto-
ionization. Indeed, multiple sharp resonances and a single
broad peak have been observed in the photodetachment spectra
of pBQ in the 2.03.0 eV region. On the basis of the order-of-
magnitude dierence in the resonances widths and estimated
excitation energies, the sharp features were assigned to
Feshbach resonances, whereas the broad band at 2.5 eV was
attributed to the 2Au shape resonance. The lifetime of the state
estimated from the width of the peak is 25 fs. Recent
computational studies of electronic structure of pBQ and pBQ
also support this assignment based on the estimates of the
vertical excitation energies of the anion.11,12 Yet, our multi-
congurational quasidegenerate perturbation theory calcula-
tions indicate that there are two bright states (2Au and 2B3u)
that absorb in this energy range. Although vertical excitation
energies dier signicantly, the adiabatic excitation energies are
very close, 2.33 and 2.39 eV for 2Au and 2B3u states, respectively
(Figure 1). The simulated shapes of the 2Au 2B2g and 2B3u
2
B2g transitions overlap signicantly (Figure S2, SI). Recent
time-resolved photoelectron spectroscopy studies of pBQ
demonstrated ultrafast decay of the metastable excited states
on a sub-40 fs time scale to the bound ground state; however,
no direct estimate of the shape resonance lifetime could be
inferred from the experiment.11 Hence, robust theoretical
prediction of the resonance position and lifetime is essential for
understanding the complex picture of competing autodetach-
ment and internal conversion in this system. This is the rst
attempt to characterize the widths of resonances in the pBQ
photodetachment spectrum from the rst principles.
We report the complex-absorbing potential equation-of-
motion coupled-cluster (CAP-EOM-EA-CCSD) calculations of
the 2Au resonance position and width. The CAP technique2932
belongs to the group of methods that transform the
Hamiltonian into a non-Hermitian one, such that a resonance
1054
Letter
emerges as a single state with a square-integrable wave function
and complex eigenvalue:
i
E = ER
2 (1)
Real and imaginary parts of the complex eigenvalue are
associated with resonance position (ER) and width (),
respectively. Specically, an imaginary potential absorbing the
outgoing tail of the resonance wave function is added to the
Hamiltonian
H = H iW (2)
where W is chosen to have quadratic form with the size of the
box dened by RX, RY, and RZ parameters
W = Wx + Wy + Wz
0, |ri| R i
Wi =
2
i = X, Y , Z
(|ri| R i) , |ri| R i (3)
The CAP-EOM-EA-CCSD approach combines the CAP
technique with the EOM-EA-CCSD formalism,3336 and,
thus, extends the capabilities of the method originally
developed for bound electronic states to the description of
scattering resonances. Diagonalization of the similarity-trans-
formed CAP-modied Hamiltonian, H = eTHeT, in the
basis of one-particle and one-hole-two-particle congurations
derived from the closed-shell CAP-HF reference, yields
complex electron attachment energies. Real and imaginary
parts of the eigenvalue give the resonance position and width,
respectively (eq 1). T are coupled-cluster substitution
operators with the corresponding amplitudes obtained by
solving CCSD equations for the CAP-modied H (eq 2).
CAP-EOM-EA-CCSD has been shown to provide accurate
estimates of resonance position and lifetime for a test set of
small molecular systems.37,38
The focus of this work is on the assignment of the resonance
feature at 2.5 eV in the photodetachment spectrum of the gas-
phase pBQ. Because the results of CAP-based calculations
depend on several user-dened parameters, for example, CAP
box size and a criterion used to extract the resonance position
and width from the -trajectories (see below), we rst discuss
the performance of the CAP-EOM-EA-CCSD method and
potential pitfalls in the interpretation of calculations. Speci-
cally, we address the following: (i) criteria for distinguishing
resonance and pseudocontinuum states (that can appear as false
resonances) based on the results of CAP-EOM-EA-CCSD
calculations and (ii) the eects of the box size (CAP onset) and
one-electron basis set in the quantitative prediction of the
resonance position and width.
The calculations were performed at the optimized ground-
state geometry of the pBQ radical anion, unless stated
otherwise. Two complementary computational approaches
have been employed. Multistate multireference perturbation
theory has been used for accurate characterization of the
energies of the ground and the two bright excited states of the
anion. The 2B3u state leading conguration can be derived from
the 1Ag reference in a two-electron excitation manner: electron
attachment to the b2g orbital and electron promotion from the
b3u to b2g orbital (Figure 1). This type of states is problematic
for the EOM-EA-CCSD method. Multireference perturbation
theory approaches, on the contrary, do not suer from this
shortcoming as all possible levels of excitations within the active
DOI: 10.1021/acs.jpclett.5b00207
J. Phys. Chem. Lett. 2015, 6, 10531058
The Journal of Physical Chemistry Letters Letter

Figure 2. -trajectories for the pseudocontinuum and resonance 2Au states. (A) Two HF MOs giving rise to the leading congurations in the target
open-shell anionic states (2Au). (B) CAP-EOM-EA-CCSD/cc-pVDZ+[24s] -trajectories for the two states that are close in energy to the
experimental resonance position (top) and changes in the amplitudes of one-particle excitations (R1, real part) into valence and diuse au orbitals
along the -trajectories. (C) CAP-EOM-EA-CCSD/cc-pVTZ+[24s] -trajectories for the two 2Au states and changes in the amplitudes of one-
particle excitations (R1, real part) into valence and diuse au orbitals along the -trajectories. RX = 8 , RY =10 , and RZ = 15 .

space are treated at the same footing. The methods, however,
do not account for the metastable character of the state. Thus,
the CAP-EOM-EA-CCSD approach has been employed to
characterize the position and the width of the 2Au resonance.
The 2Au dominant conguration is formed from the 1Ag closed
shell reference upon single electron attachment to au orbital,
and thus, the state can be reliably described with EOM-EA-
CCSD and CAP-EOM-EA-CCSD methods. Specically, the
equilibrium structure was obtained using extended multi-
reference quasidenerate perturbation theory, XMCQDPT2,39
with the daug-cc-pVTZ basis set. The model space was spanned
by ten CASSCF wave functions. The active space included all
and lone pair orbitals. State-averaging over the 10 lowest roots
was employed for the CASSCF step. The Firey package40 has
been used for the XMCQDPT2 calculations. The shapes of the
active orbitals are given in the SI (Figure S1). Frequency
analysis was performed using CASSCF with the same active
space and 6-311++G(2d,p) basis set for the molecular
geometries optimized at the same level of theory using
GAMESS(US).23 The cc-pVDZ and cc-pVTZ dunning valence
basis sets employed in the CAP-EOM-EA-CCSD calculations
were augmented by 24 additional diuse functions (+[24s]);
eight ghost atoms were located 1.45 above and below the
four ring carbon atoms, each hosting three diuse s-type
functions. This conguration of the ghost atoms ensures proper
symmetry of the resulting diuse orbitals required for coupling
with the 2Au resonance. The exponents are given in the SI.
CAP-EOM-EA-CCSD calculations were performed using the
Q-Chem package.41
Conventional EOM-EA-CCSD ( = 0) calculations yield two
Au states lying in the 2.63.6 eV energy range representing the
resonance and a discretized continuum state. The states are in-
phase and out-of-phase combinations of two congurations
corresponding to an unpaired electron occupying either a
valence or diuse au orbital (Figure 2A). Representative -
1055
trajectories, the series of eignenvalues computed for dierent
values of (eq 2), and relevant orbitals are shown in Figure 2.
Interestingly, the two states are of mixed character at = 0,
with both congurations contributing with the similar weights.
In particular, the corresponding EOM-EA-CCSD/cc-pVDZ
+[24s] weights (calculated as squares of the amplitudes shown
in Figure 2 for 22Au state) are 0.441 and 0.531 for the diuse
and valence congurations, respectively. The stronger coupling
between the valence and diuse congurations in the case of
the smaller cc-pVDZ basis can be tentatively attributed to the
incompleteness of the valence basis subset and resulting basis
functions borrowing from the diuse subset that causes a strong
mixture of valence and diuse congurations. Indeed, the eect
is less pronounced for the case of larger cc-pVTZ basis. At
larger , the valence and diuse congurations decouple as the
resonance state becomes stabilized. Note that the character of
the two orbitals is conserved along the -trajectories (SI, Figure
S3). The higher-energy state in the cc-pVDZ basis (Figure 2B)
and the lower-energy state in the cc-pVTZ basis (Figure 2C)
acquire pronounced valence-like character inherent to reso-
nance states. In contrast, the other state (the lower-energy state
in the cc-pVDZ basis and the higher-energy state in the cc-
pVTZ basis) becomes dominated by a conguration with an
electron occupying the diuse orbital and, thus, is a
pseudocontinuum state. The dierent character of the states
also manifests itself in a more compact shape of the trajectory
for the resonance state in comparison to the pseudocontinuum
one. Thus, the assignment of the states to either pseudocontin-
uum (false resonance) or true resonance states must be done
with care, taking into account both shapes of the trajectories
and the character of the wave functions.
Once the resonance state is identied, one can analyze the
trajectory and extract the resonance position and lifetime. We
used two approaches for the analysis of -trajectories. In the
rst one, the position and lifetime were extracted from the
DOI: 10.1021/acs.jpclett.5b00207
J. Phys. Chem. Lett. 2015, 6, 10531058
The Journal of Physical Chemistry Letters Letter

trajectory point corresponding to the minimum of the
trajectory velocity, |dE/d| min.29 The second approach
is a variation of the original rst-order correction suggested by
Meyer29 and is based on deperturbation of the real and
imaginary parts of the eigenvalue using rst-order perturbation
theory37
URe = E Re Tr[WI]
(4)
UIm = E Im + Tr[WR ] (5)
where W is a one-particle CAP operator dened in eq 3 and R/
I are real and imaginary parts of the one-particle CAP-EOM-
EA-CCSD target state density matrix. One then searches for the
minima of the derivative of URe and UIm with respect to
independently. Representative CAP-EOM-EA-CCSD/cc-pVDZ
+[24s] -trajectories are shown in Figure 3. One can see that
Figure 3. CAP-EOM-EA-CCSD/cc-pVDZ+[24s] -trajectory for the
2
Au resonance. (A) Corrected resonance position, ER, ER = URe
E(2B2g). Derivative of ER extracted from corrected trajectories with
respect to (B). Corrected width = 2UIm (C) and its derivative
(D). Uncorrected -trajectory, ER = ERe E(2B2g) and = 2EIm (E).
Velocity of the uncorrected trajectory (F). Arrows indicate the
stabilized resonance (position and width). RX = 8 , RY = 10 , and RZ
= 15 .
the real and imaginary parts of the corrected trajectories exhibit
minima at equal to 3.4 102 (Figure 3A,B) and 6.5 102,
respectively (Figure 3C,D). The resulting values of the
resonance position and width are 3.09 and 0.06 eV. The values
extracted from the uncorrected trajectory are close for this
system, 3.08 and 0.09 eV (Figure 3E,F).
The resonance position and width computed with the CAP-
based approach are known to depend on the CAP onset.29,37,42
The shape of the au orbital suggests that one can expect the 2Au
resonance to be most sensitive to the change of the box size in
the direction of the axis perpendicular to the molecular plane (x
axis). Thus, we xed the values of RY and RZ and gradually
increased RX from 6 to 12 with an increment of 1 . The
resulting values of the resonance position and lifetime for the
cc-pVDZ basis and boxes of various sizes are listed in Table 1.
One can see that ER and values vary from 3.13 to 3.07 and
from 0.146 to 0.027 eV, respectively. The lifetimes and
resonance positions almost do not change for RX 11 . No
stationary points on the UIm trajectories have been observed for
the boxes with RX of 11 and 12 . As follows from Table 1, the
variation in the CAP onset from 8 to 12 results in only
moderate shifts in the resonance position and width. Thus, the
results are stable with respect to this parameter starting from RX
= 8 . To quantify the eect of the valence one-electron basis
set, we performed CAP-EOM-EA-CCSD/cc-pVTZ+[24s]
calculation for one representative box size (RX = 8 ). The
results are given in Table 2 and in Figure 4. One can see that
the increase of the valence basis set signicantly improves the
description of the resonance position, whereas the width is
almost unaected. The resonance parameters extracted from
the deperturbed trajectories exhibit similar variations with CAP
onset to those obtained from the uncorrected ones. The
previous test studies of resonances in small molecules37
indicated greater stability of resonance position and width
estimated from the corrected trajectories with respect to the
CAP box size in comparison to the ones obtained using velocity
criterion applied to original trajectories. We, therefore, rely on
the former approach to derive the best estimate of the 2Au
resonance position and width. Thus, our best CAP-EOM-EA-
CCSD estimates of the 2Au resonance position and width are
2.87 and 0.013 eV, respectively. We also analyzed the
convergence of the resonance position and lifetime with the
size and the type of the diuse subset. Two bases have been
considered, [40s] and [24s8p], in which the original [24s] basis
was augmented with 2s and 1p functions at each ghost atom,
respectively. As follows from Table 2, addition of s-type basis
functions does not lead to signicant changes in resonace
position or width. Addition of p-type basis functions improves
the description of the resonance position, yet it does not aect
the width. Thus, we believe that [24s] diuse subset enables
reliable description of coupling to the continuum and
consequently the lifetimes of the resonance state.

Table 1. CAP-EOM-EA-CCSD/cc-pVDZ+[24s] Resonance Position (ER) and Width ()a

RX, URe UIm E
ER, eV opt , eV opt ER, eV , eV opt
6 3.13 1.1 102 0.146 9.0 103 3.09 0.166 6 103
7 3.099 1.5 102 0.094 2.4 102 3.09 0.120 1.34 102
8 3.085 3.4 102 0.062 6.5 102 3.08 0.085 3.7 102
9 3.076 7.0 102 0.040 2.3 101 3.077 0.061 9.0 102
10 3.073 3.0 101 0.027 8.0 101 3.074 0.044 3.0 101
11 3.067 2.9 101 3.073 0.035 8.4 101
12 3.066 4.7 101 3.072 0.033 1.2

a
The size of the CAP box is varied along the X direction (RX). RY = 10 , and RZ = 15 , unless stated otherwise.

1056 DOI: 10.1021/acs.jpclett.5b00207

J. Phys. Chem. Lett. 2015, 6, 10531058
The Journal of Physical Chemistry Letters Letter

Table 2. Energy (ER) and Width () for the 2Au Resonance of the pBQ Aniona
URe UIm E
method basis ER, eV optR , eV optIm ER, eV , eV opt
2 2
CAP-EOM-EA-CCSD cc-pVDZ+[24s] 3.09 3.4 10 0.062 6.5 10 3.08 0.085 3.7 102
CAP-EOM-EA-CCSD cc-pVDZ+[40s] 3.08 3.5 102 0.058 6.6 102 3.08 0.079 3.4 102
CAP-EOM-EA-CCSD cc-pVDZ+[24s8p] 2.97 2.4 102 0.050 4.0 102 2.98 0.094 1.6 102
CAP-EOM-EA-CCSD cc-pVTZ+[24s] 2.87 3.0 102 0.013 3.8 102 2.89 0.027 1.2 102
XMCQDPT2 daug-cc-pVTZ 2.55
experiment19 ER = 2.5; = 0.025
a
RX = 8, RY = 10, and RZ = 15 ().

stabilization technique combined with time-dependent density

Figure 4. CAP-EOM-EA-CCSD/cc-pVTZ+[24s] -trajectory for the
2
Au resonance. (A) Corrected resonance position ER = URe E(2B2g)
as a function of . (B) Corrected resonance width = 2UIm as a
function of . (C) Uncorrected -trajectory, ER = ERe E(2B2g) and
= 2EIm. RX = 8 , RY = 10 , and RZ = 15 .
Previous theoretical studies provided good estimates of the
2
Au resonance position using regular excited-state methods in
compact basis sets. However, no theoretical predictions of
resonance width for the 2Au state have been reported. Schiedt
and Weinkauf assigned the broad peak (200 cm1) at 2.5 eV to
the 2Au state based on the shape resonance character of the
state and matching energetics.19 At the same time, there is
another bright excited state of the anion at 2.5 eV, namely, the
2
B3u state. Our calculations indicate that the 2.5 eV peak in the
photodetachment spectrum can be explained solely by
autodetachment from the 2Au state on the basis of good
agreement between the computed and experimental width of
the band. The assignment is further supported by the
XMCQDPT2 results that place the 2Au shape resonance 2.55
eV above the ground state of the anion, which is in good
agreement with the position of the resonant peak in the
photodetachment spectrum (Table 2). The resonance character
of the state, however, is not taken into account in the
aforementioned calculations. The width estimate of 0.013 eV
(51 fs assuming natural line shape) is also in good agreement
with an upper bound of 27 fs for the 2Au state lifetime
accounting for both relaxation and photodetachment channels
obtained from time-dependent photoelectron spectroscopy
studies combined with a kinetic model.11 Note that our
calculations are performed for a xed nuclear conguration;
thus, one cannot anticipate a perfect agreement with the
experimental resonance width even in the limit of the exact
functional theory.20 This insensitivity of the lifetime to the
geometry might be misleading though as other structural
changes might have a pronounced eect on the lifetime.
Moreover, as autodetachment from the 2Au state and
radiationless relaxation into the ground electronic state of the
anion occur on the same femtosecond time scale, disentangling
the two competing pathways is challenging. The computational
studies reported here present the rst step toward explicit
incorporation of autoionization channels into the theoretical
description of photo- and electron-attachment-induced pro-
cesses in pBQ and biological quinones in general.
In summary, we report the rst ab initio estimate of the 2Au
photodetachment resonance width in pBQ using the CAP-
EOM-EA-CCSD method. The computed resonance position
and width enable the assignment of the 2.5 eV band in the
photodetachment spectrum of the pBQ to the 2Au shape
resonance. This broad resonance can serve as a gateway state
for both electron detachment and attachment processes in
pBQ. We have shown that the interpretation of the results
obtained with CAP-based methods should be performed with
caution. Both the character of the states and the shape of the
trajectories have to be taken into consideration for discrim-
inating between the resonance and pseudocontinuum states
when using truncated many- and one-electron bases. Notorious
CAP box size eects, being less pronounced for small
molecules, become more important for larger systems, and
both velocity criteria and deperturbed trajectories result in
box-dependent stationary points. Large valence one-electron
basis sets of at least triple- quality combined with moderate
diuse counterparts are required for accurate description of the
resonance position.
*
ASSOCIATED CONTENT
S Supporting Information
Details of XMCQDPT2 calculations, 2Au 2B2g and 2B3u
2
B2g simulated spectra, CAP-EOM-EA-CCSD/cc-pVDZ+[24s]
-trajectories for dierent box sizes and discussion of their
shapes, as well as additional results for other basis sets, the 2Au
resonance position and width for the geometry of neutral pBQ,
exponents of diuse basis functions, and equilibrium geo-
metries. This material is available free of charge via the Internet
at http://pubs.acs.org.

electronic structure model. To estimate the eects of the
geometry changes on the 2Au state lifetime, we also considered AUTHOR INFORMATION
the equilibrium geometry of the neutral pBQ. The computed
width of the 2Au resonance is 0.041 eV, which is signicantly Notes
smaller than the recent estimate of 0.346 eV obtained with the The authors declare no competing nancial interest.
1057 DOI: 10.1021/acs.jpclett.5b00207
J. Phys. Chem. Lett. 2015, 6, 10531058
The Journal of Physical Chemistry Letters
ACKNOWLEDGMENTS
We are grateful to Prof. Anna Krylov for the valuable comments
on the manuscript. The authors also thank Prof. Weinkauf for
providing photodetachment spectra for the para-benzqouinone
anion.
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