Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP

Nakata, Ayako; Imamura, Yutaka; Nakai, Hiromi

doi:10.1063/1.2227379

Cited by 78 publications

(102 citation statements)

References 33 publications

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“…[153] for a recent application to XAS calculation on liquid water), this approach does not provide very reliable spectra for deeper excitations with conventional DFT XC functionals; TDDFT heavily underestimates core excitation energies † † † , which has been shown to be caused by the self-interaction error [154] at short distances. [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.…”

Section: Valence Electron Excitationsmentioning

confidence: 99%

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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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Section: Valence Electron Excitationsmentioning

confidence: 99%

“…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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“…This error stems from the approximate exchange within the exchange-correlation functionals. 14,[18][19][20][21][22] To correct for this error, exchange correlation functionals with increased fractions of Hartree-Fock (HF) exchange, 14,18,19 a combination of exchange-correlation functionals, 23 a self-interaction correction 20,21 and excited state methods that use exact exchange, such as CIS(D), 24 have been proposed.…”

Section: Introductionmentioning

confidence: 99%

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

Besley

Peach

Tozer

2009

Phys. Chem. Chem. Phys.

201

304

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We report calculations of core excitation energies and near-edge X-ray absorption fine structure (NEXAFS) spectra computed with time-dependent density functional theory (TDDFT). TDDFT with generalized gradient approximation and standard hybrid exchange-correlation functionals is known to underestimate core excitation energies. This failure is shown to be associated with the self-interaction error at short interelectronic distances. Short-range corrected hybrid functionals are shown to reduce the error in the computed core excitation energies for first and second row nuclei in a range of molecules to a level approaching that observed in more traditional excited states calculations in the ultraviolet region. NEXAFS spectra computed with the new functionals agree well with experiment and the pre-edge features in the NEXAFS spectra of plastocyanin are correctly predicted.

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“…Core excitation energies computed with TDDFT with standard exchange-correlation functionals are known to significantly underestimate experiment. [31][32][33][34] This was addressed recently through the use of a short-range corrected functional. 35 When applied to the pre-edge features in the Cu and S K-edge spectra, the excitation energies were predicted in good agreement with experiment.…”

Section: Introductionmentioning

confidence: 99%

Modelling the spectroscopy and dynamics of plastocyanin

Robinson

Besley

2010

Phys. Chem. Chem. Phys.

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The electronic absorption, electronic circular dichroism and X-ray absorption spectroscopy of the blue copper protein plastocyanin is studied with density functional theory, time-dependent density functional theory and multireference configuration interaction in conjunction with classical molecular dynamics simulations. A strong correlation is observed between the excitation energy of the intense ligand to metal charge transfer band and the copper-cysteine sulfur bond length. The results suggest that the copper-cysteine sulfur bond length in the crystal structure of plastocyanin is too short and should be closer to the corresponding bond lengths in related blue copper proteins. Averaging over many structural conformations is required to reproduce the major features of the experimental circular dichroism spectra. A correlation between the rotational strength of the ligand to metal charge transfer band and the distortion of the copper atom from the plane of the cysteine sulfur and histidine nitrogen atoms is found. X-ray absorption calculations show a smaller sulfur p orbital character in the singly occupied molecular orbital of cucumber basic protein compared to plastocyanin.

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Hybrid exchange-correlation functional for core, valence, and Rydberg excitations: Core-valence-Rydberg B3LYP

Cited by 78 publications

References 33 publications

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

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

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

Modelling the spectroscopy and dynamics of plastocyanin

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