We have recently shown that the C-1 structure of N(OH)(3) to be more stable than the C-3 by only around 1 kcal/mol. We study here the dynamical process each of these structures follows through Born-Oppenheimer ab initio molecular dynamics simulations at room temperature, using gaussian basis sets and a hybrid exchange-correlation functional; the structural evolution of both processes lead to the discovery of a new and more stable isomer with C, symmetry. Highly-correlated calculations at the MP2, MP4 and CCSD(T) levels confirm this new structure as the absolute minimum in the global PES of N(OH)(3). (c) 2006 Published by Elsevier B.V.