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.

Lighting recommendations for the Ryan Electric Scintillator and Fireworks Program for the official dedication Niagara Falls illumination, 1925

Walter D’Arcy Ryan was born in 1870 in Kentville, Nova Scotia. He became the chief of the department of illumination at the General Electric Company of Schenectady, New York. He was a founder in the field of electrical illumination. He built the electric steam scintillator which had numerous nozzles and valves. The operator would release steam through the valves. The nozzles all had names which included: Niagara, fan, snake, plume, column, pinwheel and sunburst. The steam scintillator was combined with projectors, prismatic reflectors, flashers and filters to produce the desired effects. In 1920 a group of businessmen from Niagara Falls, New York formed a group who called themselves the “generators’. They lobbied the American and Canadian governments to improve the illumination of the Falls. They were able to raise $58, 000 for the purchase and installation of 24 arc lights to illuminate the Falls. On February 24th, 1925 the Niagara Falls Illumination Board was formed. Initially, the board had a budget of $28,000 for management, operation and maintenance of the lights. The power was supplied free by the Ontario Power Company. They had 24 lights installed in a row on the Ontario Power Company surge tank which was next to the Refectory in Victoria Park on the Canadian side. The official opening ceremony took place on June 8th, 1925 and included a light parade in Niagara Falls, New York and an international ceremony held in the middle of the Upper Steel Arch Bridge. Walter D’Arcy Ryan was the illuminating engineer and A.D. Dickerson who was his New York field assistant directed the scintillator. with information from American Technological Sublime by David E. Nye and the Niagara Falls info website Location: Brock University Archives Source Information: Subject Headings: Added Entries: 100 Ryan, W. D’A. |q (Walter D’Arcy), |d 1870-1934 610 General Electric Company 650 Lighting, Architectural and decorative 650 Lighting |z New York (State) |z Niagara Falls 700 Dickerson, A.F. 700 Schaffer, J.W. Related material held at other repositories: The Niagara Falls Museum in Niagara Falls, Ontario has a program (pamphlet) dedicating new lighting in 1958 and it has postcards depicting the illumination of the Falls. Some of Ryan’s accomplishments can be seen at The Virtual Museum of the City of San Francisco. Described by: Anne Adams Date: Sept 26,Upper Steel Arch Bridge. Walter D’Arcy Ryan was the illuminating engineer and A.D. Dickerson who was his New York field assistant directed the scintillator. with information from American Technological Sublime by David E. Nye and the Niagara Falls info website