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wright1239995101.pdf (1.24 MB)
ETD Abstract Container
Abstract Header
Electronic to Vibrational Energy Transfer from Cl
*
(
2
P
1/2
) to CH
4
and CD
4
Author Info
Munson, Brian R.
Permalink:
http://rave.ohiolink.edu/etdc/view?acc_num=wright1239995101
Abstract Details
Year and Degree
2009, Master of Science (MS), Wright State University, Chemistry.
Abstract
Electronic-to-vibrational (E-V) energy transfer is a significant kinetic channel in the collisional quenching of spin-orbit excited chlorine atoms, Cl
*
(
2
P
1/2
, 882 cm
-1
), by molecular collision partners. In the present study Cl
*
atoms are prepared in the presence of CH
4
or CD
4
, under pseudo first-order conditions, by photolysis of ICl at 532 nm with a pulsed Nd:YAG laser. Quenching of Cl
*
by CH
4
or CD
4
results in E-V excitation of the ν4 asymmetric bending mode as observed by infrared (IR) fluorescence from the vibrationally excited products. Time-resolved IR fluorescence observations of CH
4
(ν
4
) and CD
4
(ν
4
) are consistent with a simple kinetic scheme involving direct E-V excitation of CH
4
(ν
4
) or CD
4
(ν
4
) followed by a slower collisional relaxation. The total quenching rate of Cl
*
is reflected in the rise of the ν4 fluorescence signal. The Cl
*
total bimolecular quenching rate coefficients (± 2σ) obtained in this study at 298 ± 2 K are (1.9 ± 0.5) x 10
-11
cm
3
molecule
-1
s
-1
for quenching by CH
4
and (1.4 ± 0.9) x 10
-10
cm
3
molecule
-1
s
-1
for CD
4
. Intensity measurements interpreted within this kinetic scheme indicate that the E-V channel for ν4 mode excitation accounts for ≈30% of the total quenching of Cl
*
by CH
4
and CD
4
. It is remarkable that the E-V branching ratios are the same in both systems even though the ν
4
– Cl
*
energy differences span a four-fold range from approximately ½kT (CD
4
) to 2kT (CH
4
).
Committee
David Dolson, PhD (Advisor)
Paul Seybold, PhD (Committee Member)
Steven Higgins, PhD (Committee Member)
Pages
96 p.
Subject Headings
Chemistry
Keywords
E-V Energy Transfer
;
Spin-orbit excited chlorine
;
Time-resolved IR fluorescence
Recommended Citations
Refworks
EndNote
RIS
Mendeley
Citations
Munson, B. R. (2009).
Electronic to Vibrational Energy Transfer from Cl
*
(
2
P
1/2
) to CH
4
and CD
4
[Master's thesis, Wright State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=wright1239995101
APA Style (7th edition)
Munson, Brian.
Electronic to Vibrational Energy Transfer from Cl
*
(
2
P
1/2
) to CH
4
and CD
4
.
2009. Wright State University, Master's thesis.
OhioLINK Electronic Theses and Dissertations Center
, http://rave.ohiolink.edu/etdc/view?acc_num=wright1239995101.
MLA Style (8th edition)
Munson, Brian. "Electronic to Vibrational Energy Transfer from Cl
*
(
2
P
1/2
) to CH
4
and CD
4
." Master's thesis, Wright State University, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=wright1239995101
Chicago Manual of Style (17th edition)
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Document number:
wright1239995101
Download Count:
679
Copyright Info
© 2009, all rights reserved.
This open access ETD is published by Wright State University and OhioLINK.