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Infrared spectroscopy, vibrational p...

University of Pennsylvania.

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Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere./
作者:	Derro, Erika L.
面頁冊數:	266 p.
附註:	Adviser: Marsha I. Lester.
Contained By:	Dissertation Abstracts International69-09B.
標題:	Atmospheric Sciences. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3328547
ISBN:	9780549812159

Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere.
Derro, Erika L.

Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere. - 266 p.

Adviser: Marsha I. Lester.

Thesis (Ph.D.)--University of Pennsylvania, 2008.

The hydrogen trioxy (HOOO) radical has been implicated as an important intermediate in key processes in the atmosphere. In the present studies, HOOO is produced by the combination of O2 and photolytically generated OH radicals in the collisional region of a pulsed supersonic expansion. Rotationally cooled HOOO is probed in the effectively collision-free region of the expansion using infrared action spectroscopy, an infrared-pump, ultraviolet-probe technique, in which HOOO is vibrationally excited and the nascent OH products of vibrational predissociation are probed via laser-induced fluorescence.

ISBN: 9780549812159Subjects--Topical Terms:

1019179
Atmospheric Sciences.

Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere.
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100 1 $a Derro, Erika L. $3 1030711
245 1 0 $a Infrared spectroscopy, vibrational predissociation dynamics and stability of the hydrogen trioxy (HOOO) radical and estimation of its abundance in the atmosphere.
300 $a 266 p.
500 $a Adviser: Marsha I. Lester.
500 $a Source: Dissertation Abstracts International, Volume: 69-09, Section: B, page: 5427.
502 $a Thesis (Ph.D.)--University of Pennsylvania, 2008.
520 $a The hydrogen trioxy (HOOO) radical has been implicated as an important intermediate in key processes in the atmosphere. In the present studies, HOOO is produced by the combination of O2 and photolytically generated OH radicals in the collisional region of a pulsed supersonic expansion. Rotationally cooled HOOO is probed in the effectively collision-free region of the expansion using infrared action spectroscopy, an infrared-pump, ultraviolet-probe technique, in which HOOO is vibrationally excited and the nascent OH products of vibrational predissociation are probed via laser-induced fluorescence.
520 $a High resolution infrared spectra of HOOO and DOOO were observed in the fundamental and overtone OH/D stretching regions (nui and 2nu 1), which comprise a rotationally structured band attributed to the trans conformer, and an unstructured component assigned to the cis conformer. Infrared spectra of HOOO and DOOO combination bands composed of the OH stretch and a low frequency mode (nu1 + nun) were also observed. This allowed identification of vibrational frequencies for five of the six modes for trans-H/DOOO and four of the six modes for cis-HOOO and DOOO. Identification of low frequency modes provides critical information on the vibrational dynamics and thermochemical properties of the HOOO radical, and furthermore, provides a potential means for detecting HOOO in situ in the atmosphere.
520 $a In addition, the nascent OH X2pi products following vibrational predissociation of HOOO have been investigated. The product state distributions reveal a distinct preference for population of pi(A ') Λ-doublets in OH that is indicative of a planar dissociation of trans-HOOO in which the symmetry of the bonding orbital is maintained. The highest observed OH quantum state allows determination of the stability of HOOO relative to the OH + O 2 asymptote using a conservation of energy approach. In conjunction with a similar investigation of DOOO, the binding energy is determined to be ≤ 5.31 kcal/mol. The atmospheric abundance of HOOO is assessed using a statistical mechanical approach employing the experimentally determined binding energy and spectroscopic properties, which suggests that HOOO may be a significant sink for atmospheric OH radicals, specifically under the low temperature and moderate pressure conditions of the tropopause.
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650 4 $a Chemistry, Physical. $3 560527
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773 0 $t Dissertation Abstracts International $g 69-09B.
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791 $a Ph.D.
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