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Theoretical predictions of nuclear magnetic resonance parameters in a novel organo-xenon species: Chemical shifts and nuclear quadrupole couplings in HXeCCH
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10.1063/1.2805389
/content/aip/journal/jcp/127/23/10.1063/1.2805389
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/23/10.1063/1.2805389

Figures

Image of FIG. 1.
FIG. 1.

(Color online) Basis-set convergence at the nonrelativistic MP2 level for nuclear magnetic resonance chemical shift and shielding anisotropy, and nuclear quadrupole coupling constant in HXeCCH. The results are shown as a difference from the AIV basis set, which defines the zero level. For details, see Tables S2 and S3 in EPAPS (Ref. 34).

Image of FIG. 2.
FIG. 2.

(Color online) Comparison of nonrelativistic ab initio and DFT results for (a) chemical shift, (b) chemical shift for the carbon atom directly bonded to Xe, and (c) nuclear quadrupole coupling in HXeCCH. Deviations from the CCSD(T) result are shown. The AIV basis set was used (see Table I).

Image of FIG. 3.
FIG. 3.

(Color online) Convergence of the and chemical shifts (for the carbon atom directly bonded to Xe) as a function of the Xe basis set used in Dirac-Hartree-Fock–level calculations of HXeCCH. Results with the converged “” basis set taken as the zero level. For details, see Table S7 in EPAPS (Ref. 34).

Tables

Generic image for table
Table I.

Basis-set definitions in the nonrelativistic calculations. Additions to the standard FII–FIV and HII–HIV basis sets by diffuse and tight functions are denoted as “+ ” and “+ tight ,” respectively. The nomenclature means one added primitive function in all the , , and shells. “+ ” denotes additional polarization function of the indicated type.

Generic image for table
Table II.

, , and chemical shifts (in ppm) as well as and quadrupole coupling constants (in MHz and kHz, respectively) in HXeCCH calculated at ab initio electron-correlated nonrelativistic levels. The nonrelativistic CCSD(T) absolute shielding constants of the chemical shift reference systems with the AIV basis set are (in ppm) , , and .

Generic image for table
Table III.

Basis-set dependence of , , and chemical shifts (in ppm) as well as and quadrupole coupling constants (in MHz and kHz, respectively) in HXeCCH at the Dirac-Hartree-Fock level. See Table S1 in EPAPS II for details of the basis sets.

Generic image for table
Table IV.

Ab initio and density-functional theory correlation as well as basis set effects on the chemical shift in HXeCCH (in ppm). The nonrelativistic and the five main relativistic Breit-Pauli perturbation theory (BPPT) terms are shown. Results are shown at two basis set levels, AIII, where AIII is used for all nuclei, as well as , where FIVut6 is used for Xe, and HIVut2 is used for C and H. The row with “BPPT” indicates the sum of the relativistic terms and “TOTAL” denotes the sum of NR and BPPT terms, including the minor terms in Table S9 in the Supplementary Information in EPAPS (Ref. 34).

Generic image for table
Table V.

Comparison of relativistic Breit-Pauli perturbation theory (BPPT) and Dirac-Hartree-Fock (DHF) results for the , , and chemical shifts in HXeCCH (in ppm). Various combinations of ab initio and density-functional theory BPPT results are listed with the converged basis set. Final predicted results are indicated as resulting from three different models.

Generic image for table
Table VI.

Final predictions for nuclear quadrupole coupling constants of (in kHz) and (in MHz) nuclei in HXeCCH, resulting from the application of Eq. (10).

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/content/aip/journal/jcp/127/23/10.1063/1.2805389
2007-12-20
2014-04-21
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Theoretical predictions of nuclear magnetic resonance parameters in a novel organo-xenon species: Chemical shifts and nuclear quadrupole couplings in HXeCCH
http://aip.metastore.ingenta.com/content/aip/journal/jcp/127/23/10.1063/1.2805389
10.1063/1.2805389
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