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We report on the photodissociation dynamics study of n-butyl nitrite(n-C_4H_9ONO) and isoamyl nitrite ((CH_3)_2C_3H_5ONO) by means of time-resolvedFourier transform infrared (TR-FTIR) emission spectroscopy. The obtainedTR-FTIR emission spectra of the nascent NO fragments produced in the 355-nmlaser photolysis of the two alkyl nitrite species showed an almost identicalrotational temperature and vibrational distributions of NO. In addition, aclose resemblance between the two species was also found in the measuredtemporal profiles of the IR emission of NO and the recorded UV absorptionspectra. The experimental results are consistent with our ab initiocalculations using the time-dependent density functional theory at theB3LYP/6-311G(d,p) level, which indicate that the substitution of one of the two{gamma}-H atoms in n-C_4H_9ONO with a methyl group to form (CH_3)_2C_3H_5ONOhas only a minor effect on the photodissociation dynamics of the two molecules.

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