Cooperative effects in blue-shifted hydrogen bonded cluster of CF3H•••(HF)1≤n≤3 from first principles simulations

Ab initio molecular dynamics technique has been used to estimate the structural, electronic and vibrational properties of the blue-shifted hydrogen bonded CF3H center dot center dot center dot(HF)(1 <= n <= 3) complexes. Different reaction pathways and aggregation products have been studied as a function of temperature. The self-aggregation of HIF molecules and the formation of CF3H center dot center dot center dot(HF)(2) and CF3H center dot center dot center dot(HF)(3) cyclic structures have been found at the temperature of 50 K The estimated energetic cooperative effects stabilize these structures even at higher temperature which is not the case in the CF3H center dot center dot center dot(HF) complex. The structural cooperative effects manifest in the (HF)(2-3) chain formation which size determines the binding energy. The anharmonic spectra obtained from molecular dynamics simulations show the pronounced vibrational cooperative effects and might support future low temperature experiments utilizing molecular beam, supersonicjet or ultracold Helium droplet technique. (C) 2009 Elsevier B.V. All rights reserved.