Neutron study of a displacive phase transition in N-nitrodimethylamine (DMN) : High and low frequency vibrational modes; high pressure effect on the transition temperature; principal compressibilities

Abstract

N-Nitrodimethylamine is known to undergo a displacive structural phase transition at T t ∼107 K, (atmospheric pressure) associated with a soft-mode observed in the low temperature phase Raman spectrum. The soft-model has already been assigned to a lattice vibration although crystallographic observations of the symmetry breaking distortion suggest that a coupling with an internal vibration should not be ruled out. To clarify this point neutron inelastic spectra have been recorded. They lead to a better assignment of both the high and low frequency vibrations and to the conclusion that no softening of an intramolecular mode is visible. High pressure (up to 3.5 Kbars) neutron scattering experiments are also described. They give both the directions and magnitudes ( k 1=0.33× 10 −2, k b =1.17 × 10 −2, k 3 = 0.12× 10 −2Kbar −1) of the isothermal principal compressibilities of DMN and the dependence of T t on pressure ((d T t /d P) P=0 ∼ + 4.3 Kbar −1). Spectroscopic and crystallographic data now available on DMN allow us to discuss the mechanism of the transition. An extension of Samara's rule to molecular crystals is attempted