title: Examining the case for the effect of barrier compression on tunneling, vibrationally enhanced catalysis, catalytic entropy and related issues.
abstract: The idea that tunneling is enhanced by the compression of the donor-acceptor distance has attracted significant interest. In particular, recent studies argued that this proposal is consistent with pressure effects on enzymatic reactions, and that the observed pressure effects support the idea of vibrationally enhanced catalysis. However, a careful analysis of the current works reveals serious inconsistencies in the evidence presented to support these hypotheses. Apparently, tunneling decreases upon compression, and external pressure does not lead to the applicable compression of the free energy surface. Additionally, pressure experiments do not provide actual evidence for vibrationally enhanced catalysis. Finally, the temperature dependence of the entropy change in hydride transfer reactions is shown to reflect simple electrostatic effects.
authors.affiliation: Department of Chemistry (SGM418), University of Southern California, Los Angeles, CA 90089, USA.
authors.forename: Shina Caroline Lynn
authors.initials: SC
authors.lastname: Kamerlin
authors.forename: Janez
authors.initials: J
authors.lastname: Mavri
authors.forename: A
authors.initials: A
authors.lastname: Warshel
mesh_terms: D000818:Animals; D002384:Catalysis; D019277:Entropy; D006801:Humans; D007700:Kinetics; D008956:Models, Chemical; D013816:Thermodynamics