Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Autschbach, Jochen; Ziegler, Tom

doi:10.1002/3527601678.ch15

Cited by 43 publications

(31 citation statements)

References 56 publications

(120 reference statements)

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“…For explicit expressions of the perturbation operators in various approximate two-component theories see Refs. [13,14,16,[70][71][72][73] for details. Likewise, Eqn (1) contains an operator related to the presence of the nuclear spin magnetic moment vector of nucleus A, component v, which may be written asĤ…”

Section: S48mentioning

confidence: 99%

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Analyzing Pt chemical shifts calculated from relativistic density functional theory using localized orbitals: The role of Pt 5d lone pairs

2008

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Pt chemical shifts were calculated from two-component relativistic density functional theory (DFT). The shielding tensors were analyzed by using a recently developed method to decompose the spin-orbit DFT results into contributions from spin-free localized orbitals (here: natural localized molecular orbitals (NLMOs) and natural bond orbitals (NBOs)). Seven chemical shifts in six Pt complexes with Pt oxidation states II, III, and IV; and halide, amino, and amidate ligands were analyzed, with particular focus on the role of nonbonding Pt 5d orbitals. A simple d-orbital 'rotation' model has been used to rationalize some of the observed trends such as the main difference between Pt(II) and Pt(IV) chemical shifts. The localized orbital analysis data showed that most of this difference as well as trends among different Pt complexes with similar coordination can be rationalized by comparing properties of the nonbonding Pt 5d orbitals. We have also analyzed the spin-orbit effects on the chemical shifts of [PtCl4](2-) compared to [PtBr4](2-).

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Section: S48mentioning

confidence: 99%

“…Regarding theoretical methods for relativistic NMR computations, we refer the reader to Refs. [13,14] and [16] for overviews.…”

Section: Introductionmentioning

confidence: 99%

Analyzing Pt chemical shifts calculated from relativistic density functional theory using localized orbitals: The role of Pt 5d lone pairs

2008

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“…However, this coupling is the smallest from the whole set and not very relevant to the analysis based on ratios. Other near-outliers are 2 J(H-Hg) couplings in CH 2 (HgCl) 2 and CH(HgCl) 3 , having J appr. /J exact ratios 1.41 and 1.57, respectively.…”

Section: Accuracy Of the New Approach Compared To The Reference Methodsmentioning

confidence: 99%

“…Since we also implemented an approach without involving the fit of the electron densities, we can address this issue by comparing the results obtained with both approaches. We performed the calculations for a representative set of 63 indirect nuclear spin-spin couplings ( 1 J(H-H), 2 J(H-H), 1 J(H-X) (X = C, Si, Ge, Sn, Pb), 1 J(H-X) (X = F, Cl, Br, I), 2 J(H-Hg), 3 J(C-Hg), 1 J(C-X) (X = Zn, Cd, Tl, Hg, Cu, Au, Ag), 2 J(N-Cd) (X = Zn, Cd, Tl, Hg, Cu, Au, Ag), and 1 J(N-X) (X = Cu, Au, Ag)) employing both types of the exchangecorrelation kernel. The relation between exact and fitted kernel calculation is plotted in Fig.…”

Section: Accuracy Of the New Approach Compared To The Reference Methodsmentioning

confidence: 99%

“…Nowadays, with the increasing power of computers and the progress in the development of quantum chemical programs, calculations of NMR parameters in heavy-element compounds become increasingly popular. [1][2][3][4][5][6][7] Since the effects of the electron correlation are often very important for qualitative prediction of these parameters and since quite often post-Hartree-Fock calculations are still too expensive, the Density Functional Theory (DFT) turned out to be the method of choice. In recent years, significant progress in the development of relativistic methods and relativistic DFT programs was made (see, for example, an excellent review of Belpassi et al 8 ).…”

Section: Introductionmentioning

confidence: 99%

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Relativistic four-component calculations of indirect nuclear spin-spin couplings with efficient evaluation of the exchange-correlation response kernel

Křístková

Komorovský

Repiský

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inIn this work, we report on the development and implementation of a new scheme for efficient calculation of indirect nuclear spin-spin couplings in the framework of four-component matrix Dirac-Kohn-Sham approach termed matrix Dirac-Kohn-Sham restricted magnetic balance resolution of identity for J and K, which takes advantage of the previous restricted magnetic balance formalism and the density fitting approach for the rapid evaluation of density functional theory exchange-correlation response kernels. The new approach is aimed to speedup the bottleneck in the solution of the coupled perturbed equations: evaluation of the matrix elements of the kernel of the exchange-correlation potential. The performance of the new scheme has been tested on a representative set of indirect nuclear spin-spin couplings. The obtained results have been compared with the corresponding results of the reference method with traditional evaluation of the exchange-correlation kernel, i.e., without employing the fitted electron densities. Overall good agreement between both methods was observed, though the new approach tends to give values by about 4%-5% higher than the reference method. On the average, the solution of the coupled perturbed equations with the new scheme is about 8.5 times faster compared to the reference method. C 2015 AIP Publishing LLC. [http://dx

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Calculating NMR Chemical Shifts and J ‐Couplings for Heavy Element Compounds

Autschbach

2014

Encyclopedia of Analytical Chemistry

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Ab initio calculations of NMR parameters for compounds with heavy elements require a relativistic theoretical framework. Such calculations are able to reproduce experimentally observed ‘heavy atom’ effects in NMR spectroscopy quantitatively. Electron spin‐orbit (SO) coupling is a relativistic effect that leads to the ‘normal halogen dependence’ of light atom chemical shifts in the vicinity of heavy halogens. Similar effects exist for light atoms bound to heavy transition metals or f ‐block elements or heavy main group elements other than halogens. J ‐coupling constants involving heavy elements may increase by several hundred percent because of relativistic effects. The tensor properties of NMR shielding and J ‐coupling, observed routinely in solid‐state NMR, can be impacted very strongly by relativistic effects. This article discusses representative examples, provides a rationale why relativistic effects are large for atoms with high nuclear charges, and lists a selection of quantum chemistry program packages that are capable of relativistic NMR calculations.

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Relativistic Calculations of Spin–Spin Coupling Constants of Heavy Nuclei

Cited by 43 publications

References 56 publications

Analyzing Pt chemical shifts calculated from relativistic density functional theory using localized orbitals: The role of Pt 5d lone pairs

Analyzing Pt chemical shifts calculated from relativistic density functional theory using localized orbitals: The role of Pt 5d lone pairs

Relativistic four-component calculations of indirect nuclear spin-spin couplings with efficient evaluation of the exchange-correlation response kernel

Calculating NMR Chemical Shifts and J ‐Couplings for Heavy Element Compounds

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