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Carbon X-ray absorption spectra of fluoroethenes and acetone: A study at the coupled cluster, density functional, and static-exchange levels of theory
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10.1063/1.4795835
/content/aip/journal/jcp/138/12/10.1063/1.4795835
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/12/10.1063/1.4795835

Figures

Image of FIG. 1.
FIG. 1.

Molecular structure of (a) ethene, (b) vinylfluoride, (c) 1,1-difluoroethene, (d) cis-1,2-difluoroethene, (e) trifluoroethene, (f) tetrafluoroethene, and (g) acetone. Bond lengths are given in Å.

Image of FIG. 2.
FIG. 2.

X-ray absorption spectra of ethene as obtained with complex CCSD response theory using (a) a double-ζ basis set, (b) augmented with core-polarization functions for carbon, (c) a triple-ζ basis set with core-polarization functions for carbon, and (d) a relativistic setting with the basis set from (c). Energy separations between the most intense features are reported and triples corrections Δ T are given when available. All basis sets are augmented with diffuse functions for carbon and Rydberg functions at the center of the C–C bond. Contributions from the different dipole components are indicated by colored sticks.

Image of FIG. 3.
FIG. 3.

X-ray absorption spectra of 1,1-difluoroethene as obtained with complex CCSD response theory using (a) a double-ζ basis set, (b) augmented with core-polarization functions on carbon, and (c) augmented with diffuse functions on fluorine. For other details, see caption of Fig. 2 .

Image of FIG. 4.
FIG. 4.

X-ray absorption spectra of fluoroethenes as obtained using complex CCSD response theory and compared against experiment. 42 Theoretical spectra are shifted to account for basis set incompleteness, triple excitations, and relativistic effects; shifts are taken from the respective first 1s → π* transition in Table I . An additional common shift of −1.2 eV is applied, representing systematic errors not accounted for at the present level of theory.

Image of FIG. 5.
FIG. 5.

X-ray absorption spectra of vinylfluoride as obtained with a hierarchy of CPP-CC methods, the CPP-DFT method, and the 4-component STEX approach. Experimental excitation energies of the two 1s → π* transitions are included as dotted lines, and the energy interval is chosen as to include the second experimental ionization potential. 42 Results are aligned against the first experimental peak, with corresponding shifts reported next to each model label. The calculated ratios between the oscillator strengths of the π*-transitions are given as . Contributions from the different dipole components are indicated by colored sticks for CPP-CC and STEX and the explicit components of σ(ω) are presented for CPP-DFT.

Image of FIG. 6.
FIG. 6.

X-ray absorption spectra of 1,1-difluoroethene. For other details, see caption of Fig. 5 .

Image of FIG. 7.
FIG. 7.

X-ray absorption spectra of trifluoroethene. For other details, see caption of Fig. 5 .

Image of FIG. 8.
FIG. 8.

X-ray absorption spectra of acetone as obtained with the CPP-CC method for CC2 and CCSD, the CPP-DFT method with three different basis sets, and compared against experiment. 44 Results are aligned against the experimental 1s → π* excitation, with corresponding shifts reported next to each spectrum. The energy interval is chosen as to include the second, carbonyl, ionization potential from experiment. Contributions from the different dipole components are indicated by colored sticks for CC2 and CCSD, and the explicit components of σ(ω) are presented for DFT.

Tables

Generic image for table
Table I.

Carbon 1s → π* excitation energies (eV) and oscillator strengths of fluoroethenes. Estimated CCSDR(3) energetics account for basis set incompleteness (ΔTZ), triple excitations (ΔT), and relativistic effects (ΔREL), all acquired for ethene and 1,1-difluoroethene as explained in Sec. ??? .

Generic image for table
Table II.

Carbon chemical shifts (eV) of the 1s → π* transitions in vinylfluoride, 1,1-difluoroethene, and trifluoroethene. Orbital energy differences are denoted by ΔE1s and DFT and CC results refer to the CPP approach.

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/content/aip/journal/jcp/138/12/10.1063/1.4795835
2013-03-29
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Carbon X-ray absorption spectra of fluoroethenes and acetone: A study at the coupled cluster, density functional, and static-exchange levels of theory
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/12/10.1063/1.4795835
10.1063/1.4795835
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