Time-dependent density functional theory calculations of near-edge X-ray absorption fine structure with short-range corrected functionals

Besley, Nicholas A.; Peach, Michael J.; Tozer, David J.

doi:10.1039/b912718f

Cited by 194 publications

(318 citation statements)

References 74 publications

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“…For the S and Cl K-edge, the lowering of the 1s orbital has been estimated to be 5.9 eV and 7.9 eV for S and Cl, respectively. 16 However, for the 5a 1 →1a 1 transition the calculations significantly underestimate the experimental value. Furthermore, the experimental study assigns the band at 2814.1 eV to both 5a 1 →1a 1 and 2e→1a 1 when all the calculations predict a large energy difference between the two transitions.…”

Section: Methodsmentioning

confidence: 83%

“…Furthermore, there is no significant difference between the B3LYP and CAM-B3LYP results, this is similar to X-ray absorption spectroscopy where the use of a long range corrected functionals has no significant effect on the computed excitation energies. 16 Also shown in Table 2 are the transition energies computed with RI-CIS(D)/u6-311G** in conjunction with the RIMP2-cc-pVTZ auxiliary basis set. 50 For the molecules studies, this method To be widely applicable it is necessary for any method to be able to treat molecules that contain heavier nuclei.…”

Section: Methodsmentioning

confidence: 99%

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Quantum Chemical Calculations of X-ray Emission Spectroscopy

Wadey

Besley

2014

J. Chem. Theory Comput.

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110

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The calculation of X-ray emission spectroscopy with equation of motion coupled cluster theory (EOM-CCSD), time dependent density functional theory (TDDFT) and resolution of the identity single excitation configuration interaction with second order perturbation theory (RI-CIS(D)) is studied. These methods can be applied to calculate X-ray emission transitions by using a reference determinant with a core-hole, and they provide a convenient approach to compute the X-ray emission spectroscopy of large systems since all of the required states can be obtained within a single calculation removing the need to perform a separate calculation for each state. For all of the methods, basis sets with the inclusion of additional basis functions to describe core orbitals are necessary, particularly when studying transitions involving the 1s orbitals of heavier nuclei. EOM-CCSD predicts accurate transition energies when compared with experiment, however, its application to larger systems is restricted by its computational cost and difficulty in converging the CCSD equations for a core-hole reference determinant, which become increasing problematic as the size of the system studied increases. While RI-CIS(D)gives accurate transition energies for small molecules containing first row nuclei, its application to larger systems is limited by the CIS states providing a poor zeroth order reference for perturbation theory which leads to very large errors in the computed transition energies for some states. TDDFT with standard exchange-correlation functionals predicts transition energies that are much larger than experiment. Optimization of a hybrid and short-range corrected functional to predict the X-ray emission transitions results in much closer agreement with EOM-CCSD. The most accurate exchange-correlation functional identified is a modified B3LYP hybrid functional with 66% Hartree-Fock exchange, denoted B 66 LYP, which predicts X-ray emission spectra for a range of molecules including fluorobenzene, nitrobenzene, acetone, dimethyl sulfoxide and CF 3 Cl in good agreement with experiment.

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Section: Methodsmentioning

confidence: 83%

Section: Methodsmentioning

confidence: 99%

Quantum Chemical Calculations of X-ray Emission Spectroscopy

Wadey

Besley

2014

J. Chem. Theory Comput.

Self Cite

110

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“…[155] As a result, contrary to TP calculations, [134] the XAS spectra predicted by TDDFT with conventional functionals show large dependence on the functional used. [153] A perspective on TDDFT calculations for core electron spectroscopies has recently been published, see Ref.…”

Section: Valence Electron Excitationsmentioning

confidence: 92%

“…However, specially designed functionals (e.g., Refs. [154,155]) have been shown to produce good compatibility of TDLDA near-edge X-ray absorption fine structure spectra with experiment. [155] …”

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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“…[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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Time-dependent density functional theory calculations of near-edge X-ray absorption fine structure with short-range corrected functionals

Cited by 194 publications

References 74 publications

Quantum Chemical Calculations of X-ray Emission Spectroscopy

Quantum Chemical Calculations of X-ray Emission Spectroscopy

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

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

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