Abstract

This research is focused on single-collision energy transfer events between highly vibrationally excited benzene-like donor molecules and small bath molecules, CO2 and N2O in the vibrational ground level. Measuring how much energy is transferred from donors to bath molecules was accomplished by probing bath molecules scattered into specific-rotational states using a tunable Δv=0.0003 cm-1 solid state diode laser. The normalized energy transfer probability distribution function, P(E,E'), determined from energy gain information, is very useful in comparing collisional energy transfer efficiency between various collision systems. P(E,E') is also used to investigate the effects of donor and bath physical properties on collisional energy transfer. The first chapter details the C6H5F–CO2 system, which is the basis of a study on the effect of donor fluorination on strong collision energy transfer. The second chapter is about all fluorobenzene–CO2 systems, which investigates the effect of excess vibrational excitation energy of donors on supercollision energy transfer efficiency as well as donor fluorination effect. The third chapter focuses on how the physical properties of bath molecules affect supercollision energy transfer by measuring state-specific energy gain of N2O scattered into 0000, J=59−75. Instead of CO2, N2O was used as a bath molecule with a pyrazine donor to compare energy gain results of bath molecules with somewhat different physical properties. N2O and CO2 are isoelectronic and have similar mass, but N2O has a small dipole moment. Comparison of P(E,E') obtained from pyrazine–CO2, –N2O, –DCl, and –H2O systems helps to elucidate the effect of the bath physical properties on supercollision energy transfer efficiency. The last chapter is dedicated to the extension of the measurement range of N2O energy gain to the mid J states (J=37–75). In this chapter I discuss reliability of P(E,E') obtained from only high J tail as well as the correction of overall energy transfer rate constant.

Degree

PhD

College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry

Rights

http://lib.byu.edu/about/copyright/

Date Submitted

2011-03-11

Document Type

Dissertation

Handle

http://hdl.lib.byu.edu/1877/etd4281

Keywords

Collision energy transfer, Energy gain, Fluorination, Energy transfer probability, Nitrous oxide, Pyrazine, Fluorobenzene, Carbon dioxide, Energy transfer efficiency, Energy dependence

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