We investigated the photodissociation mechanism of N,N-dimethylnitrosamine (CH3)(2)NNO (DMN) by ab intio quantum chemical methods. Inspired by an earlier study we calculated two-dimensional potential energy surfaces of the SI state of DMN in its planar and pyramidal conformations. While the planar molecular geometry appears to possess no direct dissociation channel, the pyramidal configuration is dissociative yielding the products NO + (CH3)(2)N. Using wave packet dynamics on the planar SI potential energy surface the experimental absorption spectrum was well reproduced which gives indirect but strong support for the nondissociative nature of this surface. The transition from the planar to the pyramidal conformation of DMN was then investigated by an ab initio molecular dynamics method which revealed the time evolution of the geometrical parameters of the molecule up to the dissociation of the N-N bond. This occurs about 90 fs after photon excitation. The calculated minimum energy path along the N-N coordinate and the structural changes of the molecule along this coordinate provided a detailed picture of this indirect dissociation or, more specific, predissociation process via conformational change.