scholarly journals Erratum: Two-component relativistic hybrid density functional computations of nuclear spin-spin coupling tensors using Slater-type basis sets and density-fitting techniques [J. Chem. Phys. 129, 094105 (2008)]

2009 ◽  
Vol 130 (20) ◽  
pp. 209901 ◽  
Author(s):  
Jochen Autschbach
Keyword(s):  
Density Functional ◽  
Chem Phys ◽  
Spin Coupling ◽  
Basis Sets ◽  
Slater Type ◽  
Density Fitting ◽  
Two Component ◽  
Spin Spin Coupling ◽  
Hybrid Density Functional ◽  
Density Functional Computations

scholarly journals Fast hybrid density-functional computations using plane-wave basis sets

2019 ◽  
Vol 1 (1) ◽  
pp. 015009 ◽  
Author(s):  
Ivan Carnimeo ◽  
Stefano Baroni ◽  
Paolo Giannozzi
Keyword(s):  
Plane Wave ◽  
Density Functional ◽  
Basis Sets ◽  
Hybrid Density Functional ◽  
Density Functional Computations

Relativistic hybrid density functional calculations of indirect nuclear spin–spin coupling tensors — Comparison with experiment for diatomic alkali metal halides,

2009 ◽  
Vol 87 (7) ◽  
pp. 927-941 ◽  
Author(s):  
David L. Bryce ◽  
Jochen Autschbach
Keyword(s):  
Alkali Metal ◽  
Nuclear Spin ◽  
Density Functional ◽  
Dipolar Coupling ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Metal Halides ◽  
Alkali Metal Halides ◽  
Spin Spin Coupling ◽  
Hybrid Density Functional

The accurate calculation of the isotropic (Jiso) and anisotropic (ΔJ) parts of indirect nuclear spin–spin coupling tensors is a stringent test for quantum chemistry, particularly for couplings involving heavy isotopes where relativistic effects and relativity – electron correlation cross terms are expected to play an important role. Experimental measurements on diatomic molecules in the gas phase offer ideal data for testing the success of computational approaches, since the data are essentially free from intermolecular effects, and precise coupling anisotropies may be reliably extracted in favourable cases. On the basis of available experimental molecular-beam coupling-tensor parameters for diatomic alkali metal halides, we tabulate known values of Jiso and, taking rotational–vibrational corrections to the direct dipolar coupling constant into account, precise values of ΔJ are determined for the ground rovibrational state. First-principles calculations of the coupling tensors were performed using a recently developed program based on hybrid density functional theory using the two-component relativistic zeroth-order regular approximation (ZORA). Experimental trends in Jiso and ΔJ are reproduced with correlation coefficients of 0.993 and 0.977, respectively. Periodic trends in the coupling constants and their dependence on the product of the atomic numbers of the coupled nuclei are discussed. Finally, the hybrid functional method is also successfully tested against experimental data for a series of polyatomic xenon fluorides and group-17 fluorides.

Molecular orbital and 1H nuclear magnetic resonance studies of the inversion potentials of thianthrene and thioxanthene

1991 ◽  
Vol 69 (6) ◽  
pp. 927-933 ◽  
Author(s):  
Ted Schaefer ◽  
Rudy Sebastian ◽  
Christian Beaulieu
Keyword(s):  
Long Range ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Basis Set ◽  
Basis Sets ◽  
Inversion Barrier ◽  
H Nmr ◽  
Methylene Groups ◽  
Spin Spin Coupling ◽  
Split Valence

The inversion potentials, obtained from STO-3G, STO-3G(*), 3-21G, 3-21G(*), and 4-31G basis sets, are reported for thianthrene and thioxanthene, molecules in which both or only one of the methylene groups have been replaced by sulfur in 9,10-dihydroanthracene. Comparison with the available experimental data suggests that the split-valence bases lead to an overestimate, possibly by about 10 kJ/mol, of the inversion barrier in the crystal, whereas the STO-3G and STO-3G* basis sets underestimate this barrier. It appears that the inversion barrier for thianthrene is much lower in solution than in the crystal. The long-range coupling constants between the methylene and ring protons for thioxanthene in solution are consistent with an inversion barrier somewhat smaller than those obtained with the split-valence bases but rather larger than those predicted with the STO-3G basis set. The bond lengths and angles in the equilibrium structures of the two molecules, as computed with the 3-21G(*) basis, agree reasonably well with those in their crystals, except that the theoretical folding angles are smaller than measured. These discrepancies become less marked when expectation values are calculated from the theoretical inversion potentials at finite temperatures. Key words: MO calculations, inversion potentials of thianthrene and thioxanthene; 1H NMR, thioxanthene; spin–spin coupling constants, long range, in thioxanthene.

Hyperconjugation In Trialkylboranes Shown By Indirect Nuclear Spin-Spin Coupling Constants. Experimental Data And Density Functional Theory (Dft) Calculations

2005 ◽  
Vol 60 (3) ◽  
pp. 259-264 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Oleg L. Tok
Keyword(s):  
Experimental Data ◽  
Dft Calculations ◽  
Density Functional ◽  
Calculated Data ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Functional Theory ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
C Nmr

Trimethylborane (1), triethylborane (2), 1,3-dimethyl-1-boracyclopentane (3), 1-methyl-1- boracyclohexane (4), 9-methyl- and 9-ethyl-9-borabicyclo[3.1.1]nonane [5(Me) and 5(Et)], and 1- boraadamantane (6) were studied by 11B and 13C NMR spectroscopy with respect to coupling constants 1J(13C,11B) and 1J(13C,13C). Results of DFT calculations at the B3LYP/6-311+g(d,p) level of theory show satisfactory agreement with the experimental data. Hyperconjugation arising from C-C σ bonds adjacent to the tricoordinate boron atom is indicated, in particular for 1-boraadamantane (6), by the optimised calculated structures, and by the experimental and calculated data 1J(13C,13C). The calculated magnitude of 1J(13C,1H) for carbon atoms adjacent to boron becomes significantly smaller if the optimised structures suggest hyperconjugative effects arising from these C-H bonds

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