Rovibrationally Averaged Nuclear Shielding Constants in OCS

Jackowski, Karol; Jaszuński, Michał; Makulski, Włodzimierz; Vaara, Juha

doi:10.1006/jmre.1998.1555

Cited by 25 publications

(20 citation statements)

References 45 publications

(57 reference statements)

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“…Now, an improved 33 S shielding scale can be introduced assuming a value of 817(12) ppm as the absolute shielding of the sulfur nucleus in an isolated COS molecule. 10 Previous ab initio calculations showed that an increase in temperature from 300 to 330 K leads to only a small decrease in 33 S shielding of an isolated COS molecule, equal to 0.26 ppm. 10 This is roughly an order of magnitude smaller effect than precision of the 0 (COS) measurement and for this reason the influence of temperature on sulfur shielding was not analyzed.…”

Section: Resultsmentioning

confidence: 98%

“…This result was obtained using the spin-rotation constant for COS measured by a molecular-beam experiment, 5 Flygare's procedure 6 -9 and the CHF estimation of diamagnetic shielding in the free sulfur atom. Recently, the diamagnetic contribution of a COS molecule was calculated using a CCSD(T) (coupled-cluster singles, doubles and triples) method and the more accurate value of 817(12) was obtained 10 as the 33 S experimental shielding of an isolated COS molecule. A sulfur atom is terminal in an COS molecule and the electric field gradient at the 33 S nucleus is rather large (0.1877).…”

Section: Introductionmentioning

confidence: 99%

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An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

Jackowski

Makulski

Koźmiński

2002

Magnetic Reson in Chemistry

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

Jackowski

Makulski

Koźmiński

2002

Magnetic Reson in Chemistry

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“…It is now a routine procedure to include the effects of electron correlation and correlated shielding surfaces fully to second order are presently available for the nuclei in water, [5][6][7] ammonia, 5,8 phosphine, 5 and the carbon nucleus of methane. 5 Recently, noncorrelated shielding surface coefficients have been obtained for the nuclei in OCS, 9 CSe 2 , 10 and the methyl halide molecules CH 3 X͑XϭF, Cl, Br͒. 11 In the current paper we present the first nuclear shielding surfaces for the acetylene molecule.…”

Section: Introductionmentioning

confidence: 95%

Nuclear magnetic shielding in the acetylene isotopomers calculated from correlated shielding surfaces

Wigglesworth

Raynes

Kirpekar

et al. 2000

The Journal of Chemical Physics

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Articles you may be interested inCurrent density maps, magnetizability, and nuclear magnetic shielding tensors of bis-heteropentalenes. I. Dihydro-pyrrolo-pyrrole isomers Natural chemical shielding analysis of nuclear magnetic resonance shielding tensors from gauge-including atomic orbital calculations Ab initio, symmetry-coordinate and internal valence coordinate carbon and hydrogen nuclear shielding surfaces for the acetylene molecule are presented. Calculations were performed at the correlated level of theory using gauge-including atomic orbitals and a large basis set. The shielding was calculated at equilibrium and at 34 distinct geometries corresponding to 53 distinct sites for each nucleus. The results were fitted to fourth order in Taylor series expansions and are presented to second order in the coordinates. The carbon-13 shielding is sensitive to all geometrical parameters and displays some unexpected features; most significantly, the shielding at a carbon nucleus ͑C 1 , say͒ is six times more sensitive to change of the C 1 C 2 H 2 angle than it is to change of the H 1 C 1 C 2 angle. In addition, for small changes, ͑C 1 ͒ is more sensitive to the C 2 H 2 bond length than it is to the C 1 H 1 bond length. These, and other, examples of ''unexpected differential sensitivity'' are discussed. The proton shielding surface is much more as expected with ͑H 1 ͒ being most sensitive to the C 1 H 1 bond length, less so to the CC bond length and hardly at all to the C 2 H 2 bond length. The surfaces have been averaged over a very accurate force field to give values of ͑C͒, ͑H͒, and ͑D͒ for the ten isotopomers containing all possible combinations of 12 C, 13 C, 1 H, and 2 H nuclei at 0 K and at a number of selected temperatures in the range accessible to experiment. For the carbon shielding the dominant nuclear motion contribution comes from the bending at ''the other'' carbon atom with the combined stretching contributions being only 20% of those from bending. For the proton shielding it is the stretching of the CH bond containing the proton of interest which provides the major nuclear motion contribution. For ͑C͒ in H 13 C 13 CH at 300 K our best result is 117.59 ppm which is very close to the experimental value of 116.9 ͑Ϯ0.9͒ ppm. For ͑H͒ in H 13 C 13 CH at 300 K we obtain 29.511 ppm which is also in very close agreement with the experimental value of 29.277 ͑Ϯ0.001͒ ppm. Calculated values are also very close to recent, highly accurate carbon and proton isotope shifts in the ten isotopomers; carbon isotope shifts differ by no more than 10% from the measured values and proton isotope shifts are generally in even better agreement than this. The observed anomaly whereby the 13 C isotope shift in H 13 C 12 CD is greater than that in D 13 C 12 CH both with respect to H 13 C 12 CH is explained in terms of the bending contribution at ''the other'' carbon. The observed nonadditivity of deuterium isotope effects on the carbon shielding can be traced to a cross term involving second order bending.

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“…Specifically, at the extrapolated all-electron CCSD(T) level of theory (CCSD(T)/aug-cc-pCV[TQ]Z), the calculated equilibrium shielding constants of 33 S are 739.1, 796.7, and −203.5 ppm for H 2 S, OCS, and SO 2 , respectively, while the corresponding experimental values (corrected for vibrations using B3LYP/aug-cc-pCVTZ calculations) are 733.9, 834.3, and −139.6 ppm. These experimental values are relative to the shielding scale by Jackowski et al, 4,5 based on an absolute shielding of 817 (12) ppm in OCS, obtained from a measured spin-rotation constant by Reinartz and Dymanus 6 and a quantum-chemically calculated diamagnetic contribution, but without a proper treatment a) Electronic mail: t.u.helgaker@kjemi.uio.no b) Electronic mail: gauss@uni-mainz.de c) Electronic mail: gabriele.cazzoli@unibo.it d) Electronic mail: cristina.puzzarini@unibo.it of ro-vibrational effects. Based on the same OCS measurements, an absolute 33 S shielding of 843 (12) ppm had been proposed earlier by Wasylishen, Connor, and Friedrich.…”

Section: Introductionmentioning

confidence: 98%

33 S hyperfine interactions in H2S and SO2 and revision of the sulfur nuclear magnetic shielding scale

Helgaker

Gauß

Cazzoli

et al. 2013

The Journal of Chemical Physics

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Using the Lamb-dip technique, the hyperfine structure in the rotational spectra of H2(33)S and (33)SO2 has been resolved and the corresponding parameters--that is, the sulfur quadrupole-coupling and spin-rotation tensors--were determined. The experimental parameters are in good agreement with results from high-level coupled-cluster calculations, provided that up to quadruple excitations are considered in the cluster operator, sufficiently large basis sets are used, and vibrational corrections are accounted for. The (33)S spin-rotation tensor for H2S has been used to establish a new sulfur nuclear magnetic shielding scale, combining the paramagnetic part of the shielding as obtained from the spin-rotation tensor with a calculated value for the diamagnetic part as well as computed vibrational and temperature corrections. The value of 716(5) ppm obtained in this way for the sulfur shielding of H2S is in good agreement with results from high-accuracy quantum-chemical calculations but leads to a shielding scale that is about 28 ppm lower than the one suggested previously in the literature, based on the (33)S spin-rotation constant of OCS.

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Rovibrationally Averaged Nuclear Shielding Constants in OCS

Cited by 25 publications

References 45 publications

An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

Nuclear magnetic shielding in the acetylene isotopomers calculated from correlated shielding surfaces

33 S hyperfine interactions in H2S and SO2 and revision of the sulfur nuclear magnetic shielding scale

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Rovibrationally Averaged Nuclear Shielding Constants in OCS

Cited by 25 publications

References 45 publications

An improved 33S nuclear magnetic shielding scale from the gas‐phase study of COS

An improved 33S nuclear magnetic shielding scale from the gas‐phase study of COS

Nuclear magnetic shielding in the acetylene isotopomers calculated from correlated shielding surfaces

33 S hyperfine interactions in H2S and SO2 and revision of the sulfur nuclear magnetic shielding scale

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An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS

An improved ³³S nuclear magnetic shielding scale from the gas‐phase study of COS