Equilibrium information from nonequilibrium measurements in an experimental test of Jarzynski's equality.
Recent advances in statistical mechanical theory can be used to solve a fundamental problem in experimental thermodynamics. In 1997, Jarzynski proved an equality relating the irreversible work to the equilibrium free energy difference, DeltaG. This remarkable theoretical result states that it is possible to obtain equilibrium thermodynamic parameters from processes carried out arbitrarily far from equilibrium. We test Jarzynski's equality by mechanically stretching a single molecule of RNA reversibly and irreversibly between two conformations. Application of this equality to the irreversible work trajectories recovers the DeltaG profile of the stretching process to within k(B)T/2 (half the thermal energy) of its best independent estimate, the mean work of reversible stretching. The implementation and test of Jarzynski's equality provides the first example of its use as a bridge between the statistical mechanics of equilibrium and nonequilibrium systems. This work also extends the thermodynamic analysis of single molecule manipulation data beyond the context of equilibrium experiments.
Liphardt
Jan
J
Department of Chemistry, Biophysics Graduate Group, University of California, Berkeley, CA 94720, USA.
Dumont
Sophie
S
Smith
Steven B
SB
Tinoco
Ignacio
I
Bustamante
Carlos
C
D000818:Animals; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D007438:Introns; D008433:Mathematics; D009690:Nucleic Acid Conformation; D010957:Plasmids; D016053:RNA, Protozoan / Q000737:chemistry*; D016808:Tetrahymena thermophila / Q000235:genetics; D013816:Thermodynamics
D016053:RNA, Protozoan