Solid state NMR chemical shifts as an alternative to diffraction data in the determination of SIC polytypic structures

Silicon carbide, which has many polytypic modifications of a very simple and very symmetric structure, is an excellent model system for exploring, the relationship between chemical shift, long-range dipolar shielding, and crystal structure in network solids. A simple McConnell equation treatment of bond anisotropy effects in a poly type predicts chemical shifts for silicon and carbon sites which agree well with the experiment, provided that contributions from bonds up to 100 A are included in the calculation. The calculated chemical shifts depend on three factors: the layer stacking sequence, electrical centre of gravity, and the spacings between silicon and carbon layers. The assignment of peaks to lattice sites is proved possible for three polytypes (6H, 15R, and 3C). The fact that the calculated chemical shifts are very sensitive to layer spacings provides us a potential way to detennine and refine a crystal structure. In this work, the layer spacings of 6H SiC have been calculated and are within X-ray standard deviations. Under this premise, the layer spacings of 15R have been detennined. 29Si and 13C single crystal nmr studies of 6H SiC polytype indicate that all silicons and carbons are magnetically anisotropic. The relationship between a magnetic shielding tensor component and layer spacings has been derived. The comparisons between experimental and semi-empirical chemical shielding tensor components indicate that the paramagnetic shielding of silicon should be included in the single crystal chemical shift calculation.

An analysis of the methyl rotation dynamics in the So (x' A) and T (a A) states of thioacetaldehyde from Pyrolysis jet spectra /

Jet-cooled, laser-induced phosphorescence excitation spectra (LIP) of thioacetaldehyde CH3CHS, CH3CDS, CD3CHS and CD3CDS have been observed over the region 15800 - 17300 cm"^ in a continuous pyrolysis jet. The vibronic band structure of the singlet-triplet n -* n* transition were attributed to the strong coupling of the methyl torsion and aldehydic hydrogen wagging modes . The vibronic peaks have been assigned in terms of two upper electronic state (T^) vibrations; the methyl torsion mode v^g, and the aldehydic hydrogen wagging mode v^^. The electronic origin O^a^ is unequivocally assigned as follows: CH3CHS (16294.9 cm"'' ), CH3CDS (16360.9 cm"'' ), CD3CHS (16299.7 cm"^ ), and CD3CDS (16367.2 cm"'' ). To obtain structural and dynamical information about the two electronic states, potential surfaces V(e,a) for the 6 (methyl torsion) and a (hydrogen wagging) motions were generated by ab initio quantum mechanical calculations with a 6-3 IG* basis in which the structural parameters were fully relaxed. The kinetic energy coefficients BQ(a,e) , B^(a,G) , and the cross coupling term B^(a,e) , were accurately represented as functions of the two active coordinates, a and 9. The calculations reveal that the molecule adopts an eclipsed conformation for the lower Sq electronic state (a=0°,e=0"') with a barrier height to internal rotation of 541.5 cm"^ which is to be compared to 549.8 cm"^ obtained from the microwave experiment. The conformation of the upper T^ electronic state was found to be staggered (a=24 . 68° ,e=-45. 66° ) . The saddle point in the path traced out by the aldehyde wagging motion was calculated to be 175 cm"^ above the equilibrium configuration. The corresponding maxima in the path taken by methyl torsion was found to be 322 cm'\ The small amplitude normal vibrational modes were also calculated to aid in the assignment of the spectra. Torsional-wagging energy manifolds for the two states were derived from the Hamiltonian H(a,e) which was solved variationally using an extended two dimensional Fourier expansion as a basis set. A torsionalinversion band spectrum was derived from the calculated energy levels and Franck-Condon factors, and was compared with the experimental supersonic-jet spectra. Most of the anomalies which were associated with the interpretation of the observed spectrum could be accounted for by the band profiles derived from ab initio SCF calculations. A model describing the jet spectra was derived by scaling the ab initio potential functions. The global least squares fitting generates a triplet state potential which has a minimum at (a=22.38° ,e=-41.08°) . The flatter potential in the scaled model yielded excellent agreement between the observed and calculated frequency intervals.

HG 225.15-225.25 Thin Section

Dark brown sediment with sub-angular to sub-rounded grains, that range from small to medium in size. Lineations with fractured grains are abundant, and grain crushing can also be seen. Minor rotation can also be seen.

251.8-251.9 D.E #5

Sample contains well dispersed clasts ranging from small to medium in size. They are sub-angular to sub-rounded in shape. Organic rich domains can be seen throughout the sample with clear boundaries. It also contains water escape structures, seen mainly through clay. Lineations are also present.

DE #6 260.90-261.0

Coarse grained sediment with clasts ranging from small to medium in size. Clast shape range from sub-angular to sub-rounded. Lineations are present throughout the sample. Edge-to-edge grain crushing, grain stacking, and comet structures can also be seen. Some grains are crushed into one another. Areas of finer sediment can also be seen.

293.9-294.0 DE # 7

Brown sediment with well dispersed clasts. Clasts range from small to medium in size and angular to sub-rounded in shape. Some appear to have been weathered. Water escape structures can be seen, mainly in finer, clay rich sediment. Lineations can also be seen throughout the sample. Minor grain stacking and crushing are also present.

HG 316.65-316.80

Fine grained, dark brown sediment. Minor amounts of lineations can be seen. Faint water escape structures are also abundant.

HG 359.55-359.70

Dark brown sediment with mainly small clasts. The clasts range from sub-angular to sub-rounded. Lineations are abundant throughout the sample. Comet structures are also present throughout the sample. Minor amounts of grain crushing and stacking can also be seen.

384.85-385.0 DE # 11

Mainly coarse grained with a separate fine grained clay domain occurring throughout the sample. The coarse grained domain contains clasts that range from small to medium in size. The clast shape ranges from angular to sub-angular. Grain crushing is abundant in this sample, along with lineations, and minor amounts of rotation.

DE # 10 341.20-341.40

Grey sample with clasts that range from small to medium in size. The clast shape ranges from angular to sub-rounded. It mainly contains lineations and grain crushing. A few comet structures are also visible throughout the sample.

HG 388.75-388.85

Dark brown sample with clasts that range from small to large. The clast shape ranges from angular to sub-rounded. Grain crushing is present in this sample along with some lineations. Faint water escape structures can also be seen.

HG 404.20-404.30

Brown sediment with clasts ranging from small to medium in size. The clast shape ranges from angular to sub-rounded. Lineations are abundant in this sample. Faint water escape structures can also be seen as well as grain crushing/stacking.

HG 427.45-427.55

Brown sediment with grains ranging from small to large. The clast shape of this sample ranges from sub-angular to sub-rounded. Grain crushing can be seen in large amounts, and commonly involves the larger grains. Many of the larger grains are also fractured. Lineations and comet structures can also be seen.

HG 437.50-437.55

Light brown sample with clasts ranging from small to large. The clast shape ranges from sub-angular to sub-rounded. Grain crushing is common in this sample and mainly involves the larger clasts. Many grains are also crushed into one another. The larger grains are also fractured. Lineations and faint water escape structures can also be seen. This sample also contains a finer grained domain, darker in colour.

HG 445.60-445.75

Coarse grained, light brown sample with clasts ranging from small to medium in size. The clast shape ranges from sub-angular to sub-rounded. Lineations were abundant throughout the sample. A few comet structures were also found.