Vibrational overtone excitation prepares water molecules in the ‖13〉−, ‖04〉−, ‖12〉−, ‖02〉−‖2〉, and ‖03〉− local mode states for a study of the influence of reagent vibration on the endothermic bimolecular reaction H+H2O→OH+H2. The reaction of water molecules excited to the ‖04〉− vibrational state predominantly produces OH(v=0) while reaction from the ‖13〉− state forms mostly OH(v=1). These results support a spectator model for reaction in which the vibrational excitation of the products directly reflects the nodal pattern of the vibrational wave function in the energized molecule. Relative rate measurements for the three vibrational states ‖03〉−, ‖02〉−‖2〉, and ‖12〉−, which have similar total energies but correspond to very different distributions of vibrational energy, demonstrate the control that initially selected vibrations exert on reaction rates. The local mode stretching state ‖03〉− promotes the H+H2O reaction much more efficiently than either the state having part of its energy in bending excitation (‖02〉−‖2〉) or the stretching state with the excitation shared between the two O–H oscillators (‖12〉−). The localized character of the vibrational overtone excitation in water has permitted the first observation of a bond selected bimolecular reaction using this approach. The reaction of hydrogen atoms with HOD molecules excited in the region of the third overtone of the O–H stretching vibration, 4νOH, forms at least a 100‐fold excess of OD over OH, reflecting the preferential cleavage of the vibrationally excited bond.
Skip Nav Destination
Article navigation
1 April 1991
Research Article|
April 01 1991
Controlling bimolecular reactions: Mode and bond selected reaction of water with hydrogen atoms
Amitabha Sinha;
Amitabha Sinha
Department of Chemistry, University of Wisconsin–Madison, Madison, Wisconsin 53706
Search for other works by this author on:
Mark C. Hsiao;
Mark C. Hsiao
Department of Chemistry, University of Wisconsin–Madison, Madison, Wisconsin 53706
Search for other works by this author on:
F. Fleming Crim
F. Fleming Crim
Department of Chemistry, University of Wisconsin–Madison, Madison, Wisconsin 53706
Search for other works by this author on:
J. Chem. Phys. 94, 4928–4935 (1991)
Article history
Received:
November 20 1990
Accepted:
December 26 1990
Citation
Amitabha Sinha, Mark C. Hsiao, F. Fleming Crim; Controlling bimolecular reactions: Mode and bond selected reaction of water with hydrogen atoms. J. Chem. Phys. 1 April 1991; 94 (7): 4928–4935. https://doi.org/10.1063/1.460578
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Dielectric profile at the Pt(111)/water interface
Jia-Xin Zhu, Jun Cheng, et al.
Related Content
Controlling bimolecular reactions: Mode and bond selected reaction of water with translationally excited chlorine atoms
J. Chem. Phys. (January 1992)
Mechanism of the bimolecular(?) hydrogen‐iodine reaction
J. Chem. Phys. (October 1974)
Bimolecular Reaction Rates in Solids and Liquids
J. Chem. Phys. (January 1960)
Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions
J. Chem. Phys. (March 2016)
A kinetics study of the reaction of OH radicals with two C2 hydrocarbons: C2H4 and C2H2
J. Chem. Phys. (September 1975)