Accurate calculation of C1s core electron binding energies of some carbon hydrates and substituted benzenes

Takahata, Yuji; Marques, Alberto; Custódio, Rogério

doi:10.1016/j.theochem.2010.08.014

Cited by 13 publications

(10 citation statements)

References 20 publications

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“…In fact, whereas more than 20 of the DFT functionals considered here display average absolute deviations of 45 meV or better, the maximum absolute deviation does not drop below 200 meV. The largest errors in our study were found for 1,3-difluorobenzene, 1,3-pentadiene, and 1-butyne, of which the latter was not included in ref .…”

Section: Resultsmentioning

confidence: 49%

“…As applied to shifts in 89 adiabatic C1s energies in F- and CH 3 -substituted benzenes (relative to benzene), their favored approach gave an average absolute deviation (AAD) from the experimental values of 0.039 eV, which is marginally better than for the B3LYP/ECP approach described above (0.041 eV). The deviation was found to increase somewhat, to an AAD = 0.056 eV, as the chemical diversity was increased . This data set is still heavily biased however with 70% of the entries referring to F- and CH 3 -substituted benzenes.…”

Section: Introductionmentioning

confidence: 93%

“…6 To improve upon this situation, we have invested considerable effort into measuring carbon 1s ionization energies of small and medium-sized organic molecules as accurately as possible with present day electron spectrometers and third generation synchrotron light sources. The usefulness of this data set was demonstrated by Takahata and co-workers, 19 who used our experimental energies to explore the accuracy of one particular choice of exchange (PerdewÀWang 1986) and correlation (PerdewÀWang 1991) functionals to the calculation of C1s ionization energies. As applied to shifts in 89 adiabatic C1s energies in F-and CH 3 -substituted benzenes (relative to benzene), their favored approach gave an average absolute deviation (AAD) from the experimental values of 0.039 eV, which is marginally better than for the B3LYP/ECP approach described above (0.041 eV).…”

Section: Introductionmentioning

confidence: 99%

“…The deviation was found to increase somewhat, to an AAD = 0.056 eV, as the chemical diversity was increased. 19 This data set is still heavily biased however with 70% of the entries referring to F-and CH 3 -substituted benzenes.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Accuracy of Calculated Chemical Shifts in Carbon 1s Ionization Energies from Single-Reference ab Initio Methods and Density Functional Theory

Holme

Børve

Sæthre

et al. 2011

J. Chem. Theory Comput.

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A database of 77 adiabatic carbon 1s ionization energies has been prepared, covering linear and cyclic alkanes and alkenes, linear alkynes, and methyl- or fluoro-substituted benzenes. Individual entries are believed to carry uncertainties of less than 30 meV in ionization energies and less than 20 meV for shifts in ionization energies. The database provides an unprecedented opportunity for assessing the accuracy of theoretical schemes for computing inner-shell ionization energies and their corresponding chemical shifts. Chemical shifts in carbon 1s ionization energies have been computed for all molecules in the database using Hartree-Fock, Møller-Plesset (MP) many-body perturbation theory of order 2 and 3 as well as various approximations to full MP4, and the coupled-cluster approximation with single- and double-excitation operators (CCSD) and also including a perturbational estimate of the energy effect of triple-excitation operators (CCSD(T)). Moreover, a wide range of contemporary density functional theory (DFT) methods are also evaluated with respect to computing experimental shifts in C1s ionization energies. Whereas the top ab initio methods reproduce the observed shifts almost to within the experimental uncertainty, even the best-performing DFT approaches meet with twice the root-mean-squared error and thrice the maximum error compared to CCSD(T). However, a number of different density energy functionals still afford sufficient accuracy to become tools in the analysis of complex C1s photoelectron spectra.

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Section: Resultsmentioning

confidence: 49%

Section: Introductionmentioning

confidence: 93%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Accuracy of Calculated Chemical Shifts in Carbon 1s Ionization Energies from Single-Reference ab Initio Methods and Density Functional Theory

Holme

Børve

Sæthre

et al. 2011

J. Chem. Theory Comput.

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“…It is therefore highly desirable to also calculate absolute core-electron binding energies, but these are often found to differ by multiple electron volts from measured values. Some works have reported the prediction of accurate absolute core-electron binding energies , [20,[24][25][26] but this typically relies on the fortuitous cancellation of errors arising from incomplete basis sets, limitations in the treatment of exchange and correlation effects and the neglect or empirical treatment of relativistic effects [18]. The reliance on error cancellations ultimately limits the generality and the accuracy of these methods.…”

Section: Introductionmentioning

confidence: 99%

Accurate absolute core-electron binding energies of molecules, solids, and surfaces from first-principles calculations

Kahk

Lischner

2019

Phys. Rev. Materials

112

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Core-electron x-ray photoelectron spectroscopy is a powerful technique for studying the electronic structure and chemical composition of molecules, solids and surfaces. However, the interpretation of measured spectra and the assignment of peaks to atoms in specific chemical environments is often challenging. Here, we address this problem and introduce a parameter-free computational approach for calculating absolute core-electron binding energies. In particular, we demonstrate that accurate absolute binding energies can be obtained from the total energy difference of the ground state and a state with an explicit core hole when exchange and correlation effects are described by a recently developed meta-generalized gradient approximation and relativistic effects are included even for light elements. We carry out calculations for molecules, solids and surface species and find excellent agreement with available experimental measurements. For example, we find a mean absolute error of only 0.16 eV for a reference set of 103 molecular core-electron binding energies. The capability to calculate accurate absolute core-electron binding energies will enable new insights into a wide range of chemical surface processes that are studied by x-ray photoelectron spectroscopy. arXiv:1904.04823v1 [cond-mat.mtrl-sci]

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Substituent effects in chain and ring π-systems studied by core-electron binding energies calculated by density functional theory

Takahata

2011

Computational and Theoretical Chemistry

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Accurate calculation of C1s core electron binding energies of some carbon hydrates and substituted benzenes

Cited by 13 publications

References 20 publications

Accuracy of Calculated Chemical Shifts in Carbon 1s Ionization Energies from Single-Reference ab Initio Methods and Density Functional Theory

Accuracy of Calculated Chemical Shifts in Carbon 1s Ionization Energies from Single-Reference ab Initio Methods and Density Functional Theory

Accurate absolute core-electron binding energies of molecules, solids, and surfaces from first-principles calculations

Substituent effects in chain and ring π-systems studied by core-electron binding energies calculated by density functional theory

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