Measurements of the nascent NO fragments from the photodissociation of gaseous n-butyl nitrite at 266 nm were performed using the one-photon excited laser induced fluorescence technique. The rotational state distributions of the photofragment NO are found to be well characterized by a Gaussian distribution, which indicates that the photolysis process in the S, state is a direct and fast dissociation. The measured relative population of NO v '' = 0:123 is 0.65:0.19:0.11:0.05, respectively. Preferential populations of the NO Pi(+) A-doublet state and F-1((2)Pi(1/2)) spin-orbit state are observed. The TD-DFT calculations of n-butyl nitrite are in good agreement with the experimental results. (c) 2007 Elsevier B.V. All rights reserved.