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

Min Ji; Junfeng Zhen; Qun Zhang; Yang Chen

doi:10.1063/1.3129806

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

J Chem Phys. 2009 May 7;130(17):174314. doi: 10.1063/1.3129806.

Authors

Min Ji¹, Junfeng Zhen, Qun Zhang, Yang Chen

Affiliation

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, People's Republic of China.

PMID: 19425783
DOI: 10.1063/1.3129806

Abstract

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(4)H(9)ONO with a methyl group to form (CH(3))(2)C(3)H(5)ONO has only a minor effect on the photodissociation dynamics of the two molecules.