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

Coriani, Sonia; Christiansen, Ove; Fransson, Thomas; Norman, Patrick

doi:10.1103/physreva.85.022507

Cited by 171 publications

(257 citation statements)

References 46 publications

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“…This is somewhat surprising, as CCSD would be expected to be most sensitive to the quality of the basis set, but is here observed to be least Table I, where we also present earlier results at the CCSDR(3) level of theory. 66 Of the methods utilized in Fig. 1, it is clear that the CCSD spectrum is in best agreement with experiment, followed closely by TP-DFT and then by TDDFT.…”

Section: A Water Monomermentioning

confidence: 69%

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Requirements of first-principles calculations of X-ray absorption spectra of liquid water

Fransson

Zhovtobriukh

Coriani

et al. 2016

Phys. Chem. Chem. Phys.

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1 Abstract A computational benchmark study on X-ray absorption spectra of water has been performed by means of transition-potential density functional theory (TP-DFT), damped time-dependent density functional theory (TDDFT), and damped coupled cluster (CC) linear response theory. For liquid water, using TDDFT with a tailored CAM-B3LYP functional and a polarizable embedding, we find that an embedding with over 2000 water molecules is required to fully converge spectral features for individual molecules, but a substantially smaller embedding can be used within averaging schemes.TP-DFT and TDDFT calculations on 100 MD structures demonstrate that TDDFT produces a spectrum with spectral features in good agreement with experiment, while it is more difficult to fully resolve the spectral features in the TP-DFT spectrum. Similar trends were also observed for calculations of bulk ice. In order to further establish the performance of these methods, small water clusters have been considered also at the CC2 and CCSD levels of theory. Issues regarding the basis set requirements for spectrum simulations of liquid water and the determination of gas-phase ionization potentials are also discussed.2

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Section: A Water Monomermentioning

confidence: 69%

“…It is to be noted that the lack of relaxation in TDDFT remains a concern, and that the origin of the observed underestimation of the absorption cross section of CC2 for all but π-conjugated systems 66,67,99 remains an open question.…”

Section: Resultsmentioning

confidence: 99%

Requirements of first-principles calculations of X-ray absorption spectra of liquid water

Fransson

Zhovtobriukh

Coriani

et al. 2016

Phys. Chem. Chem. Phys.

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“…A method based on damped coupled cluster response has been created [5] to calculate X-ray absorption values and, for CCSD response, agrees well with experiment for neon, carbon monoxide and water. This approach would be expected to work well when the ground state is not considered multireference.…”

Section: Introductionmentioning

confidence: 92%

Multireference X-ray emission and absorption spectroscopy calculations from Monte Carlo configuration interaction

Coe

Paterson

2015

Theor Chem Acc

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We adapt the method of Monte Carlo configuration interaction to calculate core-hole states and use this for the computation of X-ray emission and absorption values. We consider CO, CH 4 , NH 3 , H 2 O, HF, HCN, CH 3 OH, CH 3 F, HCl and NO using a 6-311G** basis. We also look at carbon monoxide with a stretched geometry and discuss the dependence of its results on the cutoff used. The Monte Carlo configuration interaction results are compared with EOM-CCSD values for X-ray emission and with experiment for X-ray absorption. Oscillator strengths are also computed and we quantify the multireference nature of the wavefunctions to suggest when approaches based on a single reference would be expected to be successful.

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“…Within TD-DFT, core excitations are accessible by restricting the space of occupied-virtual orbital excitations (restricted-channel approximation) [29,30], by selectively targeting excitations within a specific energy window [31][32][33][34], by using a complex polarization propagator [35,36], or with real-time TD-DFT methods [37]. Recently, coupled-cluster response theory has also been extended to X-ray spectroscopy [38,39].…”

Section: Introductionmentioning

confidence: 99%

Origin-independent calculation of quadrupole intensities in X-ray spectroscopy

Bernadotte

Atkins

Jacob

2012

The Journal of Chemical Physics

147

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For electronic excitations in the ultraviolet and visible range of the electromagnetic spectrum, the intensities are usually calculated within the dipole approximation, which assumes that the oscillating electric field is constant over the length scale of the transition. For the short wavelengths used in hard X-ray spectroscopy, the dipole approximation may not be adequate. In particular, for metal K-edge X-ray absorption spectroscopy (XAS), it becomes necessary to include higher-order contributions. In quantum-chemical approaches to X-ray spectroscopy, these socalled quadrupole intensities have so far been calculated by including contributions depending on the square of the electric-quadrupole and magnetic-dipole transition moments. However, the resulting quadrupole intensities depend on the choice of the origin of the coordinate system. Here, we show that for obtaining an originindependent theory, one has to include all contributions that are of the same order in the wave vector consistently. This leads to two additional contributions depending on products of the electric-dipole andelectric-octupole and of the electric-dipole and magnetic-quadrupole transition moments, respectively. We have implemented such an origin-independent calculation of quadrupole intensities in XAS within timedependent density-functional theory, and demonstrate its usefulness for the calculation of metal and ligand K-edge XAS spectra of transition metal complexes.2

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

Cited by 171 publications

References 46 publications

Requirements of first-principles calculations of X-ray absorption spectra of liquid water

Requirements of first-principles calculations of X-ray absorption spectra of liquid water

Multireference X-ray emission and absorption spectroscopy calculations from Monte Carlo configuration interaction

Origin-independent calculation of quadrupole intensities in X-ray spectroscopy

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