Photolysis of n-butyl nitrite and isoamyl nitrite at 355 nm: A time-resolved Fourier transform infrared emission spectroscopy and ab initio study

Journal Article · Thu May 07 00:00:00 EDT 2009 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3129806· OSTI ID:21559707

Min, Ji; Junfeng, Zhen; Qun, Zhang; Yang, Chen ^[1]

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1. Hefei National Laboratory for Physical Sciences at the Microscale and Department of Chemical Physics, University of Science and Technology of China, Hefei, Anhui 230026 (China)

We report on the photodissociation dynamics study of n-butyl nitrite and isoamyl nitrite by means of time-resolved Fourier transform infrared (TR-FTIR) emission spectroscopy. The obtained TR-FTIR emission spectra of the nascent NO fragments produced in the 355 nm laser photolysis of the two alkyl nitrite species showed an almost identical rotational temperature and vibrational distributions of NO. In addition, a close resemblance between the two species was also found in the measured temporal profiles of the IR emission of NO and the recorded UV absorption spectra. The experimental results are consistent with our ab initio calculations using the time-dependent density functional theory at the B3LYP/6-311G(d,p) level, which indicate that the substitution of one of the two {gamma}-H atoms in n-C{sub 4}H{sub 9}ONO with a methyl group to form (CH{sub 3}){sub 2}C{sub 3}H{sub 5}ONO has only a minor effect on the photodissociation dynamics of the two molecules.

• OSTI ID: 21559707
• Journal Information: Journal of Chemical Physics, Vol. 130, Issue 17; Other Information: DOI: 10.1063/1.3129806; (c) 2009 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION SPECTRA
ATOMS
DENSITY FUNCTIONAL METHOD
DISSOCIATION
DISTRIBUTION
EMISSION
EMISSION SPECTRA
EMISSION SPECTROSCOPY
FOURIER TRANSFORMATION
INFRARED SPECTRA
LASERS
NITRIC OXIDE
NITRITES
ORGANIC COMPOUNDS
PHOTOLYSIS
REACTION KINETICS
TIME DEPENDENCE
TIME RESOLUTION
ULTRAVIOLET SPECTRA
CALCULATION METHODS
CHALCOGENIDES
CHEMICAL REACTIONS
DECOMPOSITION
INTEGRAL TRANSFORMATIONS
KINETICS
NITROGEN COMPOUNDS
NITROGEN OXIDES
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
RESOLUTION
SPECTRA
SPECTROSCOPY
TIMING PROPERTIES
TRANSFORMATIONS
VARIATIONAL METHODS