A nonequilibrium molecular dynamics (MD) study of the vibrational relaxation of the amide I mode of deuterated N-methylacetamide (NMAD) in aqueous (D(2)O) solution is carried out using instantaneous normal modes (INMs). The identification of the INMs as they evolve over time, which is necessary to analyze the energy fluxes, is made by using a novel algorithm which allows us to assign unequivocally each INM to an individual equilibrium normal mode (ENM) or to a group of ENMs during the MD simulations. The time evolution of the energy stored in each INM is monitored and the occurrence of resonances during the relaxation process is then investigated. The decay of the amide I mode, initially excited with one vibrational quantum, is confirmed to fit well to a biexponential function, implying that the relaxation process involves at least two mechanisms with different rate constants. By freezing the internal motions of the solvent, it is shown that the intermolecular vibration-vibration channel to the bending modes of the solvent is closed. The INM analysis reveals then the existence of a major and faster decay channel, which corresponds to an intramolecular vibrational redistribution process and a minor, and slower, decay channel which involves the participation of the librational motions of the solvent. The faster relaxation pathway can be rationalized in turn using a sequential kinetic mechanism of the type P-->M+L-->L, where P (parent) is the initially excited amide I mode, and M (medium) and L (low) are specific midrange and lower-frequency NMAD vibrational modes, respectively.

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We present the synthesis and oxoanion-assembling properties of a monomer with a naphthalene ring as a central core decorated with two arms containing iodotriazolium rings as anion binding sites. Interactions with SO, HPO, and HPO anions, via a cooperative mechanism, afforded new supramolecular materials stabilized by a combination of halogen- and hydrogen-bonding interactions. H NMR experiments and solid-state structure provided evidence for the initial formation of a supramolecular linear chain, nucleation step, and then two different supramolecular chains are interpenetrated with each other, elongation steps, involving the formation of hydrogen bonds between two oxygens of the anion from one of the chains and the naphthalene inner protons from the other chain. Scanning electron microscopy studies revealed that the morphology of the crystals changed dramatically with the nature of the anion added.

Nonequilibrium molecular dynamics (MD) simulations and instantaneous normal mode (INMs) analyses are used to study the vibrational relaxation of the C-H stretching modes (ν(s)(CH₃)) of deuterated N-methylacetamide (NMAD) in aqueous (D2O) solution. The INMs are identified unequivocally in terms of the equilibrium normal modes (ENMs), or groups of them, using a restricted version of the recently proposed Min-Cost assignment method. After excitation of the parent ν(s)(CH₃) modes with one vibrational quantum, the vibrational energy is shown to dissipate through both intramolecular vibrational redistribution (IVR) and intermolecular vibrational energy transfer (VET). The decay of the vibrational energy of the ν(s)(CH₃) modes is well fitted to a triple exponential function, with each characterizing a well-defined stage of the entire relaxation process. The first, and major, relaxation stage corresponds to a coherent ultrashort (τ(rel) = 0.07 ps) energy transfer from the parent ν(s)(CH₃) modes to the methyl bending modes δ(CH₃), so that the initially excited state rapidly evolves into a mixed stretch-bend state. In the second stage, characterized by a time of 0.92 ps, the vibrational energy flows through IVR to a number of mid-range-energy vibrations of the solute. In the third stage, the vibrational energy accumulated in the excited modes dissipates into the bath through an indirect VET process mediated by lower-energy modes, on a time scale of 10.6 ps. All the specific relaxation channels participating in the whole relaxation process are properly identified. The results from the simulations are finally compared with the recent experimental measurements of the ν(s)(CH₃) vibrational energy relaxation in NMAD/D₂O(l) reported by Dlott et al. (J. Phys. Chem. A 2009, 113, 75.) using ultrafast infrared-Raman spectroscopy.

The use of the Ehrenfest method to simulate the relaxation of molecules in solution is explored. Using the cyanide ion dissolved in water as a test model, the independent trajectory (IT) and the bundle of trajectories (BT) approximations are shown to provide very different results for the time evolution of the vibrational populations of the solute. None of these approximations reproduce the Boltzmann equilibrium vibrational populations accurately. A modification of the Ehrenfest method based on the use of quantum correction factors is thus proposed to solve this problem. The simulations carried out using the modified Ehrenfest method provide IT and BT relaxation times which are closer to each other and which agree quite well with previous hybrid perturbative results.