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.

Tintype of Young African American Woman Seated at Table [n.d.]

Black and white tintype of an unidentified woman seated with hand-colored red detail on her scarf and the tablecloth. The date, location and photographer are unknown. This tintype was in the possession of Iris Sloman Bell, of St. Catharines, Ontario. Relatives of the Bell - Sloman families include former slaves from the United States who escaped to Canada. They later settled in the London and St. Catharines areas of southern Ontario."Tintypes were the invention of Prof. Hamilton Smith of Ohio. They begin as thin sheets of iron, covered with a layer of black paint. This serves as the base for the same iodized collodion coating and silver nitrate bath used in the ambrotype process. First made in 1856, millions were produced well into the twentieth century. When tintypes were finished in the same sorts of mats and cases used for ambrotypes, it can be almost impossible to distinguish which process was used without removing the image to examine the substrate." Source: American Museum of Photography http://www.photographymuseum.com/primer.html

Report of a select committee to whom were referred the petition of Samuel Thompson and John Dailey: January 14, 1817, read, and ordered to lie upon the table (1817)

Concerning the request of the petitioners, former residents of Newark (present-day Niagara-on-the-Lake) in Upper Canada, for relief for the loss of their property when they were compelled to flee Canada after having aided the United States Army in the War of 1812.

Vintage/Drinkability Table

A table indicating the vintage, full bloom, notes on climate conditions and history for three types of wine. Also a rating for each vintage and drinkability (quality) rating on first page.

Printed blank from Grand Trunk Railway for shipping to St. Catharines from Buffalo for table

Printed blank from Grand Trunk Railway for shipping to St. Catharines from Buffalo for table, 1888.

Bill from Geoghegan and Co. Importers of Table Linen and Shirt and Stock Makers

Bill from Geoghegan and Co. Importers of Table Linen and Shirt and Stock Makers for clothing including cravats and hosiery, June 23, 1847 attached to receipt for Receipt from Family Linen Drapery, Shirt and Stock Warehouse, London England for payment on account, July 7, 1847.