Non-equilibrium phenomena and molecular reaction dynamics: mode space, energy space and conformer space

David R. Glowacki*, Robert Lightfoot, Jeremy N. Harvey

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

14 Citations (Scopus)
304 Downloads (Pure)

Abstract

The ability to characterise and control matter far away from equilibrium is a frontier challenge facing modern science. In this article, we sketch out a heuristic structure for thinking about the different ways in which non-equilibrium phenomena can impact molecular reaction dynamics. Our analytical schema includes three different regimes, organised according to increasing dynamical resolution: at the lowest resolution, we have conformer phase space, at an intermediate resolution, we have energy space; and at the highest resolution, we have mode space. Within each regime, we discuss practical definitions of non-equilibrium phenomena, mostly in terms of the corresponding relaxation timescales. Using this analytical framework, we discuss some recent non-equilibrium reaction dynamics studies spanning isolated small-molecule ensembles, gas-phase ensembles and solution-phase ensembles. This includes new results that provide insight into how non-equilibrium phenomena impact the solution-phase alkenehydroboration reaction. We emphasise that interesting non-equilibrium dynamical phenomena often occur when the relaxation timescales characterising each regime are similar. In closing, we reflect on outstanding challenges and future research directions to guide our understanding of how non-equilibrium phenomena impact reaction dynamics.

Original languageEnglish
Pages (from-to)631-640
Number of pages10
JournalMolecular Physics
Volume111
Issue number5
Early online date28 Feb 2013
DOIs
Publication statusPublished - 16 Apr 2013

Keywords

  • molecular dynamics
  • reaction kinetics
  • non-equilibrium
  • theoretical chemistry
  • PHASE BIMOLECULAR REACTIONS
  • TRANSITION-STATE THEORY
  • CN RADICAL REACTIONS
  • MASTER EQUATION
  • NONSTATISTICAL DYNAMICS
  • VIBRATIONAL-RELAXATION
  • CHEMICAL-REACTIONS
  • ENZYME CATALYSIS
  • COMPUTER-SIMULATIONS
  • ALKENE HYDROBORATION

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