Beyond microscopic reversibility

Are observable nonequilibrium processes precisely reversible?

Divesh Bhatt, Daniel Zuckerman

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

Although the principle of microscopic reversibility has been studied for many decades, there remain ambiguities in its application to nonequilibrium processes of importance to chemistry, physics, and biology. Examples include whether protein unfolding should follow the same pathways and in the same proportions as folding and whether unbinding should likewise mirror binding. Using continuum-space calculations which extend previous kinetic analyses, we demonstrate formally that the precise symmetry of forward and reverse processes is expected only under certain special conditions. Approximate symmetry will be exhibited under a separate set of conditions. Exact, approximate, and broken symmetry scenarios are verified in several ways: using numerical calculations on toy and molecular systems; using exact calculations on kinetic models of induced fit in protein-ligand binding; and based on reported experimental results. The analysis highlights intrinsic challenges and ambiguities in the design and the analysis of both experiments and simulations.

Original languageEnglish (US)
Pages (from-to)2520-2527
Number of pages8
JournalJournal of Chemical Theory and Computation
Volume7
Issue number8
DOIs
StatePublished - Aug 9 2011
Externally publishedYes

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symmetry
ambiguity
Proteins
Kinetics
proteins
design analysis
kinetics
Mirrors
Physics
Ligands
biology
folding
broken symmetry
proportion
chemistry
mirrors
continuums
ligands
physics
Experiments

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Beyond microscopic reversibility : Are observable nonequilibrium processes precisely reversible? / Bhatt, Divesh; Zuckerman, Daniel.

In: Journal of Chemical Theory and Computation, Vol. 7, No. 8, 09.08.2011, p. 2520-2527.

Research output: Contribution to journalArticle

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