Calculated spin-spin coupling surfaces in the water molecule; prediction and analysis of J(O, H), J(O, D) and J(H, D) in water isotopomers

Wigglesworth, Richard D.; Raynes, W.T.; Sauer, Stephan P. A.; Oddershede, Jens

doi:10.1080/00268979809482379

Cited by 92 publications

(45 citation statements)

References 2 publications

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“…We have carried out state of the art ab initio calculations on the above mentioned compounds using the second order polarization propagator approximation with coupled cluster single and double amplitudes (SOPPA(CCSD)) [15,25] and our aug-cc-pVTZ-J basis sets [15,16]. Previous applications of this method gave results in very good agreement with experiment [15,16,[26][27][28][29][30][31][32][33].…”

Section: Introductionsupporting

confidence: 55%

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Provasi

Aucar

Sauer

2003

IJMS

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Ab initio calculations of the spin-spin coupling constants have been carried out for methan-and ethanimine, methanal-and ethanaloxime at the level of the second order polarization propagator approximation with coupled cluster singles and doubles amplitudes (SOPPA(CCSD)) using the aug-cc-pVTZ-J basis sets. Previously we have shown that this method can reproduce quantitatively the coupling constants for methanimine; our new results for methanal-and ethanaloxime agree also very well with the measured couplings. A study of both purely geometrical and substituent effects on all coupling constants in the title compounds is presented. Analyzing the four contributions to the coupling constants we find that the stereoelectronic effect of the nitrogen lone pair on the one-bond C-H and C-C couplings as well as the corresponding effect for the geminal N-H and N-C couplings is affected strongly by the -OH substituent. For the one-bond C-N couplings we observe that the orbital paramagnetic (OP) contribution is comparable to the Fermi Contact (FC) contribution but opposite in sign and that the spin-dipolar (SD) term amounts to between 40% and 85% of the total coupling constants. Changes in the total one-bond C-N couplings caused by the -OH substituent are also almost entirely due to SD contribution.

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Section: Introductionsupporting

confidence: 55%

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Provasi

Aucar

Sauer

2003

IJMS

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“…vibrational corrections, and the solvent shift. Although vibrational corrections of one-bond X-H coupling constants can amount up to 5%, [33] for two-or three-bond couplings, they are typically less than 1 Hz as shown in recent calculations on Pyrrole, Furan and Thiophene. [34] Similarly, it is known that the solvent shifts for two-or three-bond couplings are typically very small.…”

Section: Resultsmentioning

confidence: 96%

Structural trends of ⁷⁷Se¹H spin–spin coupling constants and conformational behavior of 2‐substituted selenophenes

Rusakov

Krivdin

Sauer

et al. 2009

Magnetic Reson in Chemistry

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Experimental measurements and second-order polarization propagator approach (SOPPA) calculations of (77)Se-(1)H spin-spin coupling constants together with theoretical energy-based conformational analysis in the series of 2-substituted selenophenes have been carried out. A new basis set optimized for the calculation of (77)Se-(1)H spin-spin coupling constants has been introduced by extending the aug-cc-pVTZ-J basis for selenium. Most of the spin-spin coupling constants under study, especially vicinal (77)Se-(1)H couplings, demonstrated a remarkable stereochemical behavior with respect to the internal rotation of the substituent in the 2-position of the selenophene ring, which is of major importance in the stereochemical studies of the related organoselenium compounds.

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“…To further complicate the theoretical study of indirect spin-spin coupling constants, the vibrations of the molecular framework have been shown to give significant contributions to the indirect spin-spin coupling constants, often giving contributions that are 5-10% of the magnitude of the purely electronic contributions. Recent developments have however made it possible to obtain quite accurate estimates for the vibrational corrections to the spin-spin coupling constants [21,22], even for fairly large molecules such as benzene [23]. Even if all the factors affecting the theoretical calculation of indirect spin-spin coupling constants now can be addressed for medium-sized molecules [4], a direct comparison of the theoretical results with experimental observations is in general not possible since most experimental NMR studies take place in solution.…”

Section: Introductionmentioning

confidence: 99%

Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach

Ruud

Frediani

Cammi

et al. 2003

IJMS

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Abstract:We present an extension of the Polarizable Continuum Model (PCM) to the calculation of solvent effects on indirect spin-spin coupling constants for HartreeFock wave functions and Density Functional Theory. This is achieved by implementing the PCM model for singlet and triplet linear response functions. The new code is used for calculating the solvent effects on the indirect spin-spin coupling constants of benzene. For the 1 J(H 13 C) coupling constants, our calculated solvent shifts are in good agreement with experimental observations when geometry relaxation is taken into account. However, our results do not support the extrapolated gas-phase value for this coupling constant. A new experimentally derived 1 J(H 13 C) for a vibrating benzene molecule at 300 K is proposed.

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Calculated spin-spin coupling surfaces in the water molecule; prediction and analysis of J(O, H), J(O, D) and J(H, D) in water isotopomers

Cited by 92 publications

References 2 publications

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Structural trends of ⁷⁷Se¹H spin–spin coupling constants and conformational behavior of 2‐substituted selenophenes

Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach

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Calculated spin-spin coupling surfaces in the water molecule; prediction and analysis of J(O, H), J(O, D) and J(H, D) in water isotopomers

Cited by 92 publications

References 2 publications

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

The Effect of Substituents on Indirect Nuclear Spin-Spin Coupling Constants: Methan- and Ethanimine, Methanal- and Ethanaloxime

Structural trends of 77Se1H spin–spin coupling constants and conformational behavior of 2‐substituted selenophenes

Solvent Effects on the Indirect Spin–Spin Coupling Constants of Benzene: The DFT-PCM Approach

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Structural trends of ⁷⁷Se¹H spin–spin coupling constants and conformational behavior of 2‐substituted selenophenes