Relativistic effects on the NMR parameters of Si, Ge, Sn, and Pb alkynyl compounds: Scalar versus spin-orbit effects

Demissie, Taye B.

doi:10.1063/1.4996712

Cited by 27 publications

(28 citation statements)

References 57 publications

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“…In summary, the expressions (43)- (45) have the correct collinear limit, are rotationally invariant, and numerically stable. Crucially, they are consistent with the noncollinear ansatz of Scalmani and Frisch in all cases in which the expressions (22) and (25) are well defined in the limit (s → 0 ∧ g ns → 0). Furthermore, they are equivalent, in the closed shell limit, to the well behaved kernel of Bast et al 32 .…”

Section: Please Cite This Article As Doi:101063/15121713supporting

confidence: 82%

“…This leads to additional expressions involving the Dirac delta function. For example, the exchange-correlation potential (22) should have an additional term 53…”

Section: Please Cite This Article As Doi:101063/15121713mentioning

confidence: 99%

“…18,19 Furthermore, the present authors have demonstrated that a four-component methodology is applicable to systems with up to 100 atoms, for calculation of nuclear magnetic resonance and electron paramagnetic resonance parameters. [20][21][22][23][24] Relativistic approaches to LR-TDDFT can be loosely classified using a combination of two criteria. The a) Electronic mail: stanislav.komorovsky@savba.sk first criterion is the method by which SOC and other relativistic effects are accounted for.…”

Section: Introductionmentioning

confidence: 99%

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Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems

Komorovský

Cherry

Repiský

2019

The Journal of Chemical Physics

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We present a formulation of relativistic linear response time-dependent density functional theory for calculation of electronic excitation energies in the framework of the four-component Dirac-Coulomb Hamiltonian. This approach is based on the noncollinear ansatz originally developed by Scalmani and Frisch [J. Chem. Theory Comp. 8, 2193 (2012)], and improves upon past treatment of the limit cases in which the spin density approaches zero. As a result of these improvements, the presented approach is capable of treating both closed-and open-shell reference states. Robust convergence of the Davidson-Olsen eigenproblem algorithm for open-shell reference states was achieved through the use of a solver which considers both left and right eigenvectors. The applicability of the present methodology on both closed-and open-shell reference states is demonstrated on calculations of low-lying excitation energies for Group 3 atomic systems (Sc 3+-Ac 3+) with non-degenerate ground states, as well as for Group 11 atomic systems (Cu-Rg) and octahedral actinide complexes (PaCl 2− 6 , UCl − 6 , and NpF 6) with effective doublet ground states. Major developments in the field of relativistic LR-TDDFT methods featuring variational inclusion of SOC began with the independent works of Gao et al. 29 in the four-component framework, and Wang and Ziegler 30 in the two-component framework. Both works combine noncollinear DFT theory with the ALDA approximation.

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Section: Please Cite This Article As Doi:101063/15121713supporting

confidence: 82%

“…This leads to additional expressions involving the Dirac delta function. For example, the exchange-correlation potential (22) should have an additional term 53…”

Section: Please Cite This Article As Doi:101063/15121713mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems

Komorovský

Cherry

Repiský

2019

The Journal of Chemical Physics

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“…The difference between the values obtained for HC≡CXH 3 C≡ . We note that although a different approach has been used in the recent study of HC≡CX(CH 3 ) 3 acetylene derivatives [20] the values of the computed constants (except for Sn-compound) are in between our results for HC≡CXH 3 and HC≡CX(C 2 H 5 ) 3 derivatives.…”

Section: The Influence Of the Substitution Of H Atoms With Ethylene Gsupporting

confidence: 50%

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

2018

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The nuclear spin-spin coupling constants in a series of acetylene derivatives HC≡CXH 3 , where X is C, Si, Ge, Sn, Pb, have been calculated employing both coupled-cluster theory (CC) and density functional theory (DFT), the latter in nonrelativistic and relativistic four-component approach with different exchange-correlation functionals and basis sets. In addition, property derivatives with respect to molecular geometry parameters have been computed with nonrelativistic and relativistic Hamiltonians in order to evaluate the usefulness of the calculated nonrelativistic vibrational corrections. Generally, the CC method reproduces the experimental values somewhat better than DFT. In the case of the latter, the performance of B3LYP functional was the most satisfactory. The relativistic effects become noticeable for the couplings including heavy atom in tin-and lead-containing molecules. The calculations of the derivatives of the coupling constants indicate that these derivatives are even more sensitive to the relativistic effects than the corresponding coupling constants.

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“…Further rows were not evaluated due to the difficulty of modeling heavy atoms without considering relativistic effects. [32][33][34]…”

Section: Pyrimidine Analogsmentioning

confidence: 99%

Observation of untoward ³J_cc correlations in 1,1‐ADEQUATE spectra of pyrimidine analogs: Avoiding potential interpretation pitfalls

Kim

Saurí

Cohen

et al. 2018

Magnetic Reson in Chemistry

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Recently, it has been reported that large J correlations can sometimes be observed in 1,1-ADEQUATE spectra with significant intensity, which opens the possibility of structural misassignment. In this work, we have focused on pyrimidine-based compounds, which exhibit multiple bond correlations in the 1,1-ADEQUATE experiment as a consequence of J coupling constants greater than 10 Hz. Results are supported by both the experimental measurement of J coupling constants in question using J-modulated-ADEQUATE and density functional theory calculations.

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Relativistic effects on the NMR parameters of Si, Ge, Sn, and Pb alkynyl compounds: Scalar versus spin-orbit effects

Cited by 27 publications

References 57 publications

Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems

Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

Observation of untoward ³J_cc correlations in 1,1‐ADEQUATE spectra of pyrimidine analogs: Avoiding potential interpretation pitfalls

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Relativistic effects on the NMR parameters of Si, Ge, Sn, and Pb alkynyl compounds: Scalar versus spin-orbit effects

Cited by 27 publications

References 57 publications

Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems

Four-component relativistic time-dependent density-functional theory using a stable noncollinear DFT ansatz applicable to both closed- and open-shell systems

Spin–spin coupling constants in $$\hbox {HC}{\equiv }\hbox {CXH}_3$$ HC ≡ CXH 3 molecules; $$\hbox {X}{=

Observation of untoward 3Jcc correlations in 1,1‐ADEQUATE spectra of pyrimidine analogs: Avoiding potential interpretation pitfalls

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Observation of untoward ³J_cc correlations in 1,1‐ADEQUATE spectra of pyrimidine analogs: Avoiding potential interpretation pitfalls