High energy vibrational excitations of nitromethane in liquid water
Rights accessOpen Access
All rights reserved. This work is protected by the corresponding intellectual and industrial property rights. Without prejudice to any existing legal exemptions, reproduction, distribution, public communication or transformation of this work are prohibited without permission of the copyright holder
The pathways and timescales of vibrational energy flow in nitromethane are investigated in both gas and condensed phases using classical molecular mechanics, with a particular focus on relaxation in liquid water. We monitor the flow of excess energy deposited in vibrational modes of nitromethane into the surrounding solvent. A marked energy flux anisotropy is found when nitromethane is immersed in liquid water, with a preferential flow to those water molecules in contact to the nitro group. The factors that permit such anisotropic energy relaxation are discussed, along with the potential implications on the molecule's non-equilibrium dynamics. In addition, the energy flux analysis allows us to identify the solvent motions responsible for the uptake of solute energy, confirming the crucial role of water librations. Finally, we also show that no anisotropic vibrational energy relaxation occurs when nitromethane is surrounded by argon gas.
CitationJurado, A. [et al.]. High energy vibrational excitations of nitromethane in liquid water. "The Journal of chemical physics", 15 Maig 2023, vol. 158, núm. 19, article 194501, p. 1-16.