Electronic structure of monosubstituted benzenes and X-ray emission spectroscopy

Yumatov, V. D.; Окотруб, А. В.; Fürin, G. G.; Salakhutdinov, N. F.

doi:10.1007/bf02505672

Cited by 11 publications

(16 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Also shown are the values observed in experiment. 15,[64][65][66][67][68] This provides a measure of the capability of the calculations to predict the spectra with the correct absolute energy scale. The transition energies computed with the B3LYP functional are too low, and the extent that the experimental values are underestimated increases with the nuclear charge of the absorbing atom.…”

Section: Computational Detailsmentioning

confidence: 99%

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

Hanson‐Heine

George

Besley

2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

The effect of basis set and exchange-correlation functional on time-dependent density functional theory calculations within the Tamm The accuracy of non-resonant and resonant (resonant inelastic X-ray scattering) X-ray emission spectra simulated based upon Kohn-Sham density functional theory is assessed. Accurate non-resonant X-ray emission spectra with the correct energy scale are obtained when short-range corrected exchangecorrelation functionals designed for the calculation of X-ray absorption spectroscopy are used. It is shown that this approach can be extended to simulate resonant inelastic X-ray scattering by using a reference determinant that describes a core-excited state. For this spectroscopy, it is found that a standard hybrid functional, B3LYP, gives accurate spectra that reproduce the features observed in experiment. However, the ability to correctly describe subtle changes in the spectra arising from different intermediate states is more challenging and requires averaging over conformations from a molecular dynamics simulation. Overall, it is demonstrated that accurate non-resonant and resonant X-ray emission spectra can be simulated directly from Kohn-Sham density functional theory.

show abstract

Section: Computational Detailsmentioning

confidence: 99%

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

Hanson‐Heine

George

Besley

2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Experimental data. [58][59][60][61] S indicates satellite lines due to multielectron processes and the theoretical spectrum for CF 3 Cl has been shifted by +7.9 eV to account for relativistic effects.…”

Section: Referencesmentioning

confidence: 99%

Quantum Chemical Calculations of X-ray Emission Spectroscopy

Wadey

Besley

2014

J. Chem. Theory Comput.

110

View full text Add to dashboard Cite

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.

show abstract

“…This work continues a series of our publications [1][2][3] concerned with the C=O chemical bond in a number of compounds and its manifestations in X ray emission spectra. The purpose of this work was to obtain the X ray emission spectrum of acetaldehyde, perform quantum chemical calculations, construct theoretical spectra on their basis, and, as a result, identify the experimental data.…”

Section: Introductionmentioning

confidence: 64%

Ultrasoft X-ray emission and the electronic structure of the acetaldehyde molecule

Davydova

Yumatov

2012

Russ. J. Phys. Chem.

Self Cite

View full text Add to dashboard Cite

The electronic structure of the acetaldehyde molecule was studied by the ultrasoft X ray emission method with the use of quantum chemical calculations. The OK α and CK α spectra of the compound in the gas phase were obtained. Quantum chemical calculations were performed at the RHF/6 311++G** level. The calculation results were used to construct theoretical X ray spectra. The experimental spectra are inter preted.

show abstract

Electronic structure of monosubstituted benzenes and X-ray emission spectroscopy

Cited by 11 publications

References 12 publications

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

Kohn-Sham density functional theory calculations of non-resonant and resonant x-ray emission spectroscopy

Quantum Chemical Calculations of X-ray Emission Spectroscopy

Ultrasoft X-ray emission and the electronic structure of the acetaldehyde molecule

Contact Info

Product

Resources

About