High Resolution Infrared Spectroscopy of Spiropentane and Bicyclopentane
EMSL Project ID
32692
Abstract
The structures and physical properties of small organic strained-ring systems are of interest to both experimental and theoretical chemists. The object of the proposed research is to apply high-resolution infrared and Raman/CARS spectroscopic methods to the determination of accurate structural and rovibrational parameters of gaseous spiropentane and bicyclopentane and to compare these with values obtained from high level quantum calculations. Prior work by the collaborators on cyclopropane and propellane have shown that detailed modeling of the rich rovibronic features of the spectra of such small symmetric-top molecules can give more reliable and accurate molecular parameters than have been available in the past. These results, and those anticipated in this study, are particularly useful as bench mark data for ab initio calculations and can improve our understanding of chemical bonding. In the case of spiropentane, the bond angles about the central carbon deviate significantly from the normal sp3 values and quantum predictions of these angles and of the vibrations involving central atom motion will be examined. For propellane, the novel central bond produces an unusual electron distribution about the axial atoms and it will be interesting to compare the changes in spectral and quantum properties with corresponding values in bicyclopentane, where the central bond is lost. Key elements in this work will be the FTIR facilities at PNNL and the coherent Raman spectrometer at OSU since each gives the resolution (0.002 cm-1) needed to resolve individual rovibronic transitions. The analysis of the often complex rotation-vibration bands will benefit from the expertise of the collaborators in high-resolution infrared and Raman spectroscopy. Much of the work will involve the participation of students, who will be trained in an advanced area of physical chemistry in preparation for graduate studies or employment in academia, industry, or government laboratories.
Project Details
Project type
Exploratory Research
Start Date
2008-12-16
End Date
2009-12-20
Status
Closed
Released Data Link
Team
Principal Investigator
Team Members
Related Publications
Maki AG, JE Price, J Harzan, JW Nibler, A Weber, T Masiello, and TA Blake. 2015. "Analysis of several high-resolution infrared bands of spiropentane, C5H8." PNNL-SA-111275, Pacific Northwest National Laboratory, Richland, WA. doi:10.1016/j.jms.2015.03.013 [Unpublished]
Martin MA, AJ Perry, T Masiello, KD Schwartz, JW Nibler, A Weber, A Maki, and TA Blake. 2010. "High Resolution Infrared Spectra of Bicyclo [1.1.1]pentane." Journal of Molecular Spectroscopy 262(1):42-48. doi:10.1016/j.jms.2010.04.010
Perry AJ, MA Martin, JW Nibler, AG Maki, A Weber, T Masiello, and TA Blake. 2012. "Coriolis Analysis of Several High-Resolution Infrared Bands of Bicyclo[1.1.1]pentane–d0 and -d1- ." PNNL-SA-87628, Pacific Northwest National Laboratory, Richland, WA.
Price JE, KA Coulterpark, T Masiello, JW Nibler, A Weber, AG Maki, and TA Blake. 2011. "High-Resolution Infrared Spectra of Spiropentane, C5H8." Journal of Molecular Spectroscopy 269(1):129-136. doi:10.1016/j.jms.2011.05.011