Core-level electronic spectra in ADC(2) approximation for polarization propagator: Carbon monoxide and nitrogen molecules

Trofimov, A. B.; Moskovskaya, T. É.; Gromov, Evgeniy V.; Vitkovskaya, N. M.; Schirmer, J.

doi:10.1007/bf02742009

Cited by 61 publications

(76 citation statements)

References 26 publications

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“…The fundamental motivation for such approximation, originally proposed by Cederbaum, Domcke, and Schirmer,18 lies in the large difference in energy and in the localization in space between core and valence orbitals. The CVS approximation was first implemented within the algebraic diagrammatic construction [19][20][21] scheme 22,23 and later extended to TD-DFT approaches. also been presented in recent years.…”

Section: Introductionmentioning

confidence: 99%

Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework

Coriani

Koch

2015

The Journal of Chemical Physics

218

328

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Accurate ab initio based multisheeted double many-body expansion potential energy surface for the three lowest electronic singlet states of The Journal of Chemical Physics 126, 074309 (2007); 10.1063/1.2566770Erratum: "Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework" [J. Chem. Phys. 143, 181103 (2015) Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework We present a simple scheme to compute X-ray absorption spectra (e.g., near-edge absorption fine structure) and core ionisation energies within coupled cluster linear response theory. The approach exploits the so-called core-valence separation to effectively reduce the excitation space to processes involving at least one core orbital, and it can be easily implemented within any pre-existing coupled cluster code for low energy states. We further develop a perturbation correction that incorporates the effect of the excluded part of the excitation space. The correction is shown to be highly accurate. Test results are presented for a set of molecular systems for which well converged results in full space could be generated at the coupled cluster singles and doubles level of theory only, but the scheme is straightforwardly generalizable to all members of the coupled cluster hierarchy of approximations, including CC3. C 2015 AIP Publishing LLC.[http://dx

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Section: Introductionmentioning

confidence: 99%

Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework

Coriani

Koch

2015

The Journal of Chemical Physics

218

328

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“…It is followed by a sequence of much weaker discrete bands associated to Rydberg transitions: first, the 1s → 3sσ band at about 292.4 eV (C) and 539 eV (O) and second, the 1s → 3pπ band at 293.3 eV (C) and 540 eV (O). A series of high-resolution experiments [16,[43][44][45][46][47] have clarified the vibrational progressions of such transitions, but this aspect is beyond the scope of the present work.…”

Section: Carbon Monoxidementioning

confidence: 97%

“…Note that, for the C 1s → π * band, Triguero et al [14] reported, using the DFT-TP method, nonrelativistic results for the excitation energies between 287.5 and 288.9 eV, with oscillator strengths between 0.162 and 0.164, depending on the functional adopted. With a revised ADC(2) approach in combination with the core-valence separation (CVS) approximation, Trofimov et al [16] [14] results are between 535.1 and 536.1 eV (f = 0.066), ADC(2) yields 532.53 eV and 0.07 [16], the QRHF/EA-EOMCCSD method [50] gives 533.98 eV and 0.031, and its open-shell variant [50] yields 534.15 eV and 0.083. Similar to water, using the CPP approach at the TDDFT level, Ekström et al [20,21] reported an absorption spectrum for the C edge qualitatively consistent with the experimental spectrum, but with shifts of as much as +4.8 eV (LB94) and +14.8 eV (CAM-B3LYP) and weaker intensity.…”

Section: Carbon Monoxidementioning

confidence: 99%

“…Several quantum mechanical methods are available for the calculation of core-electron excitation spectra, for instance the multiple scattering MSX α technique [11], the direct static exchange method STEX [12,13], the transition potential density functional theory (DFT-TP) method [14], the algebraic diagrammatic connection [15] propagator approaches ADC(2) [16] and ADC(3) [17], various methodologies based on timedependent density-functional theory (TDDFT) [18][19][20][21], and the GW/Bethe-Salpeter equation approach [22]. Some of the proposed methods are adapted to specific systems, elements or x-ray adsorption edges, which represents an unphysical dichotomy of methodologies.…”

Section: Introductionmentioning

confidence: 99%

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Coupled-cluster response theory for near-edge x-ray-absorption fine structure of atoms and molecules

et al. 2012

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, Coupled-cluster response theory for near-edge x-ray-absorption fine structure of atoms and molecules, 2012, Physical Review A. Atomic, Molecular, and Optical Physics, (85) Based on an asymmetric Lanczos-chain subspace algorithm, damped coupled cluster linear response functions have been implemented for the hierarchy of coupled cluster (CC) models including CC with single excitations (CCS), CC2, CC with single and double excitations (CCSD), and CCSD with noniterative triple corrected excitation energies CCSDR(3). This work is a first step toward the extension of these theoretical electronic structure methods of well-established high accuracy in UV-vis absorption spectroscopies to applications concerned with x-ray radiation. From the imaginary part of the linear response function, the near K-edge x-ray absorption spectra of neon, water, and carbon monoxide are determined and compared with experiment. Results at the CCSD level show relative peak intensities in good agreement with experiment with discrepancies in transition energies due to incomplete treatment of electronic relaxation and correlation that amount to 1-2 eV. With inclusion of triple excitations, errors in energetics are less than 0.9 eV and thereby capturing 90%, 95%, and 98% of the relaxation-correlation energies for C, O, and Ne, respectively.

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“…33 Initially a 6-311++G(2d,2p) basis set was used as in a previous N 2 XPS study. 34 Photo-ionization was approximated by excitation of the core electrons into unbound Rydberg states. For this purpose a diffuse s function with orbital exponent 0.0001 was added to the basis.…”

Section: Theoretical Calculationsmentioning

confidence: 99%

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

Valov

Luerßen

Mutoro

et al. 2011

Phys. Chem. Chem. Phys.

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Nitrogen is often used as an inert background atmosphere in solid state studies of electrode and reaction kinetics, of solid state studies of transport phenomena, and in applications e.g. solid oxide fuel cells (SOFC), sensors and membranes. Thus, chemical and electrochemical reactions of oxides related to or with dinitrogen are not supposed and in general not considered. We demonstrate by a steady state electrochemical polarisation experiments complemented with in situ photoelectron spectroscopy (XPS) that at a temperature of 450 1C dinitrogen can be electrochemically activated at the three phase boundary between N 2 , a metal microelectrode and one of the most widely used solid oxide electrolytes-yttria stabilized zirconia (YSZ)-at potentials more negative than E = À1.25 V. The process is neither related to a reduction of the electrolyte nor to an adsorption process or a purely chemical reaction but is electrochemical in nature. Only at potentials more negative than E = À2 V did new components of Zr 3d and Y 3d signals with a lower formal charge appear, thus indicating electrochemical reduction of the electrolyte matrix. Theoretical model calculations suggest the presence of anionic intermediates with delocalized electrons at the electrode/electrolyte reaction interface. The ex situ SIMS analysis confirmed that nitrogen is incorporated and migrates into the electrolyte beneath the electrode.

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Core-level electronic spectra in ADC(2) approximation for polarization propagator: Carbon monoxide and nitrogen molecules

Cited by 61 publications

References 26 publications

Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework

Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework

Coupled-cluster response theory for near-edge x-ray-absorption fine structure of atoms and molecules

Electrochemical activation of molecular nitrogen at the Ir/YSZ interface

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