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Methyl nitrite and tert-butyl nitrite have been photolyzed in their charge transfer $\ast$ bands at $44,400cm-1$. The nascent internal energy distribution of the resulting NO fragment was monitored via $2+2$ multiphoton ionization spectroscopy. The NO rotational distribution of both nitrites appeared to be bimodal, with a colder Boltzmann portion overlapped by a high energy tail. The total rotational energy was calculated to be $1050cm-1$. NO was not formed in states higher than $v\prime \prime =0$.