Time-dependent density functional theory calculations of the spectroscopy of core electrons

Besley, Nicholas A.; Asmuruf, Frans A.

doi:10.1039/c002207a

Cited by 244 publications

(394 citation statements)

References 121 publications

(190 reference statements)

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“…[94][95][96] Additionally, the SIE can be accounted for by use of the self-interaction correction (SIC), both for ionization potentials 97 and excitation energies. 98 In the present study we will refrain from using either the specially tailored functionals or the SIC, as we argue that the absolute energetics are of less interest than the relative energetics -the SIC has been observed to vary by, at most, 0.2 and 0.4…”

Section: B Linear Response Theorymentioning

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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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: B Linear Response Theorymentioning

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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“…[153] A perspective on TDDFT calculations for core electron spectroscopies has recently been published, see Ref. [156]. ERKALE currently supports calculations only at the timedependent LDA (TDLDA) level ‡ ‡ ‡ .…”

Section: Valence Electron Excitationsmentioning

confidence: 99%

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

et al. 2012

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ERKALE is a novel software program for computing X-ray properties, such as ground-state electron momentum densities, Compton profiles, and core and valence electron excitation spectra of atoms and molecules. The program operates at Hartree-Fock or density-functional level of theory and supports Gaussian basis sets of arbitrary angular momentum and a wide variety of exchange-correlation functionals. ERKALE includes modern convergence accelerators such as Broyden and ADIIS and it is suitable for general use, as calculations with thousands of basis functions can routinely be performed on desktop computers. Furthermore, ERKALE is written in an object oriented manner, making the code easy to understand and to extend to new properties while being ideal also for teaching purposes.

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“…Within the context of quantum chemical calculations, core-electron binding energies (CEBEs) are most commonly computed using a self-consistent field ( SCF) approach [6][7][8][9], although an unrestricted generalised transition state method has also been proposed for the calculation of CEBEs [10,11]. X-ray absorption spectra can be computed using the transition potential method [12], time-dependent density functional theory (TDDFT) [13,14], Bethe-Salpeter equation [15], coupled cluster theory [16,17], the algebraic diagrammatic construction (CVS-ADC) scheme [18] and multi-reference methods [19]. TDDFT and EOM-CCSD methods have also been used to study X-ray emission spectroscopy through the use of a reference determinant with a core-hole [20][21][22][23].…”

Section: Introductionmentioning

confidence: 99%

Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

Fouda

Besley

2017

Theor Chem Acc

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The performance of Gaussian basis sets for density functional theory-based calculations of core-electron spectroscopies is assessed. The convergence of core-electron binding energies and core-excitation energies using a range of basis sets including split-valence, correlation-consistent, polarisation-consistent and individual gauge for localised orbitals basis sets is studied. For self-consistent field calculations of core-electron binding energies and core-excitation energies of first-row elements, relatively small basis sets can accurately reproduce the values of much larger basis sets, with the IGLO basis sets performing particularly well. Calculations for the K-edge of second-row elements are more challenging, and of the smaller basis sets, pcSseg-2 has the best performance. For the correlation-consistent basis sets, inclusion of core-valence correlation functions is important, with the cc-pCVTZ basis set giving accurate results. Time-dependent density functional theory-based calculations of core-excitation energies show less sensitivity to the basis set with relatively small basis sets, such as pcSseg-1 or pcSseg-2, reproducing the values for much larger basis sets accurately. In contrast, time-dependent density functional theory calculations of X-ray emission energies are highly dependent on the basis set, but the IGLO-II, IGLO-III and pcSseg-2 basis sets provide a good level of accuracy.

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Time-dependent density functional theory calculations of the spectroscopy of core electrons

Cited by 244 publications

References 121 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

ERKALE—A flexible program package for X‐ray properties of atoms and molecules

Assessment of basis sets for density functional theory-based calculations of core-electron spectroscopies

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