Vibrational potential energy functions and conformations of 2-cyclopenten-1-one and other carbonyl-containing compounds in their ground and excited electronic states /

Bibliographic Details
Main Author: Cheatham, Charles Michael, 1963-
Other Authors: Fry, Edward S. (degree committee member.), Hedges, Richard M. (degree committee member.), Lucchese, Robert R. (degree committee member.)
Format: Thesis Book
Language:English
Published: 1990.
Subjects:
Online Access:Link to OAKTrust copy

MARC

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040 |a TXA  |b eng  |c TXA  |d OCLCQ  |d OCLCO  |d UMI  |d OCLCF  |d TXA 
035 |a (OCoLC)24007049 
049 |a TXAM 
099 |a 1990  |a Dissertation  |a C514 
100 1 |a Cheatham, Charles Michael,  |d 1963- 
245 1 0 |a Vibrational potential energy functions and conformations of 2-cyclopenten-1-one and other carbonyl-containing compounds in their ground and excited electronic states /  |c by Charles Michael Cheatham. 
264 1 |c 1990. 
300 |a xiii, 182 leaves :  |b illustrations ;  |c 29 cm 
336 |a text  |b txt  |2 rdacontent 
337 |a unmediated  |b n  |2 rdamedia 
338 |a volume  |b nc  |2 rdacarrier 
500 |a Typescript (photocopy). 
502 |b Ph. D.  |c Texas A & M University  |d 1990 
500 |a Vita. 
504 |a Includes bibliographical references. 
500 |a "Major subject: Chemistry." 
520 3 |a The far-infrared spectra of 2-cyclopenten-1-one and its 5-d₁and 5, 5-d₂derivatives have been recorded and analyzed. The fundamental ring-puckering frequencies were observed at 94.4, 89.0, and 84.9 cm⁻¹, respectively, for the d₀, d₁, and d₂ species. In addition to the main puckering series for each molecule, side bands arising from the ring-twisting excited states were also observed. Ring-twisting bands from various puckering states were observed for all three species in the 280 to 290 cm⁻¹ region. The data demonstrate that the molecular skeleton is planar. A two-dimensional potential energy function of the form V = a₁x₁⁴ + b₁x₂² + a₂x₂⁴ + b₂x₂² + cx₁²x₂², where x₁ and x₂ are the ring-puckering and ring-twisting coordinates, was determined. For all three isotopomers this gives rise to calculated frequencies which are in excellent agreement with the observed values. The interaction term c is larger than in related molecules, reflecting the effects of asymmetry and conjugation. A computer-controlled apparatus for laser-induced fluorescence excitation spectroscopy (FES) of jet-cooled samples has been constructed and optimized, particularly in terms of nozzle and optical design. FES spectra of the S₁ (n, π*) states of 2-cyclopenten-1-one and its 5,5-d₂ isotopomer have been recorded in the 370 to 340 nm region. The electronic origin for the undeuterated species occurs at 27210 cm⁻¹. The vibrational frequencies for the three carbonyl motions and the nine ring modes were observed for the excited state. Bands at 67, 158, and 256 cm⁻¹ for the d₀ species, at 63, 147, and 240 cm⁻¹ for the 5-d₁ isotopomer, and at 59, 138, and 227 cm⁻¹ for the d₂ species were assigned to the ring-puckering motion in the S₁ state. A single one-dimensional potential energy function accurately fit the data for all three isotopomers. This function is nearly purely quartic in character and shows the ring to be planar in the electronic excited state. However, it has become less rigid, and this is ascribed to be a decrease in initial angle strain within the ring. The C = 0 and C = C stretching frequencies occur at 1418 and 1357 cm⁻¹ for the d₀ molecule. The S₁ (n, π*) FES spectra of propanal-d₀, propanal-2,2-d₂, propanal-1-d₁, and propynal have also been recorded in order to continue the study of the effects of conjugation on molecular conformations in ground and excited electronic states. 
650 0 |a Molecules  |x Vibration  |x Analysis. 
650 0 |a Electronic excitation. 
650 0 |a Spectrum analysis. 
650 7 |a Electronic excitation.  |2 fast  |0 (OCoLC)fst00907192 
650 7 |a Spectrum analysis.  |2 fast  |0 (OCoLC)fst01129108 
650 4 |a Chemistry 
655 7 |a Academic theses  |2 lcgft 
700 1 |a Laane, Jaan,  |e degree supervisor. 
700 1 |a Fry, Edward S.,  |e degree committee member. 
700 1 |a Hedges, Richard M.,  |e degree committee member. 
700 1 |a Lucchese, Robert R.,  |e degree committee member. 
710 2 |a Texas A & M University,  |e degree granting institution. 
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