eprintid: 16082
rev_number: 16
userid: 1291
dir: disk0/00/01/60/82
datestamp: 2012-10-29 21:28:36
lastmod: 2019-02-02 15:56:12
status_changed: 2012-10-29 21:28:36
type: article
metadata_visibility: show
item_issues_count: 0
eprint_status: archive
creators_name: Agbo, JK
creators_name: Leitner, DM
creators_name: Myshakin, EM
creators_name: Jordan, KD
creators_email: 
creators_email: 
creators_email: 
creators_email: jordan@pitt.edu
creators_id: 
creators_id: 
creators_id: 
creators_id: JORDAN
title: Quantum energy flow and the kinetics of water shuttling between hydrogen bonding sites on trans-formanilide
ispublished: pub
divisions: sch_as_chemistry
full_text_status: public
abstract: A potential energy surface for trans-formanilide (TFA)- H2 O is calculated and applied to study energy flow in the complex as well as the kinetics of water shuttling between hydrogen bonding sites on TFA. In addition to the previously identified H2 O-TFA (CO) and H2 O-TFA (NH) minima, with the water monomer bound to the CO and NH groups, respectively, the new surface reveals a second local minimum with the water bound to the CO group, and which lies energetically 310 cm-1 above the previously identified H2 O-TFA (CO) global minimum. On this surface, the energy barrier for water shuttling from H2 O-TFA (CO) global minimum to H2 O-TFA (N-H) is 984 cm-1, consistent with the experimental bounds of 796 and 988 cm-1 [J. R. Clarkson Science 307, 1443 (2005)]. The ergodicity threshold of TFA is calculated to be 1450 cm-1; for the TFA- H2 O complex, the coupling to the water molecule is found to lower the ergodicity threshold to below the isomerization barrier. Energy transfer between the activated complex and the vibrational modes of TFA is calculated to be sufficiently rapid that the Rice-Ramsperger-Kassel-Marcus (RRKM) theory does not overestimate the rate of water shuttling. The possibility that the rate constant for water shuttling is higher than the RRKM theory estimate is discussed in light of the relatively high energy of the ergodicity threshold calculated for TFA. © 2007 American Institute of Physics.
date: 2007-08-20
date_type: published
publication: Journal of Chemical Physics
volume: 127
number: 6
refereed: TRUE
issn: 0021-9606
centers: cen_other_molecularmatsim
id_number: 10.1063/1.2754689
pmid: 17705604
mesh_headings: Chemistry, Physical--methods
mesh_headings: Electrons
mesh_headings: Energy Transfer
mesh_headings: Formamides--chemistry
mesh_headings: Hydrogen Bonding
mesh_headings: Kinetics
mesh_headings: Models, Chemical
mesh_headings: Models, Theoretical
mesh_headings: Molecular Conformation
mesh_headings: Molecular Structure
mesh_headings: Peptides--chemistry
mesh_headings: Quantum Theory
mesh_headings: Thermodynamics
mesh_headings: Water--chemistry
chemical_names: Formamides
chemical_names: Peptides
chemical_names: N-phenylformamide
chemical_names: Water
citation:   Agbo, JK and Leitner, DM and Myshakin, EM and Jordan, KD  (2007) Quantum energy flow and the kinetics of water shuttling between hydrogen bonding sites on trans-formanilide.  Journal of Chemical Physics, 127 (6).   ISSN 0021-9606     
document_url: http://d-scholarship-dev.library.pitt.edu/16082/1/licence.txt