Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(nOH) +H2(nHH)→H2O+H

Donald G. Truhlar; Alan D. Isaacson

doi:10.1063/1.444297

Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(n_OH) +H₂(n_HH)→H₂O+H

Donald G. Truhlar, Alan D. Isaacson

Chemistry (Twin Cities)

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Abstract

The state-selected reaction rates OH(n_OH = 0,1) + H ₂(n_HH = 0,1)→H₂O + H are calculated by an extension of variational transiton state theory. The reactant vibrational modes are assumed to correlate diabatically with generalized normal modes of a generalized activated complex. Using the Walch-Dunning-Schatz-Elgersma ab initio potential energy surface, the theory predicts that excitation of H₂ is 19-68 times more effective than excitation of OH in promoting reaction at 300 K, where the range of values corresponds to different possible assumptions about the quantal effects on reaction-coordinate motion. These values are in much better agreement with the experimental value (about 100) than is a calculation based on the conventional transition state, which yields 2 × 10⁴.

Original language	English (US)
Pages (from-to)	3516-3522
Number of pages	7
Journal	The Journal of chemical physics
Volume	77
Issue number	7
DOIs	https://doi.org/10.1063/1.444297
State	Published - 1982

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title = "Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(nOH) +H2(nHH)→H2O+H",

abstract = "The state-selected reaction rates OH(nOH = 0,1) + H 2(nHH = 0,1)→H2O + H are calculated by an extension of variational transiton state theory. The reactant vibrational modes are assumed to correlate diabatically with generalized normal modes of a generalized activated complex. Using the Walch-Dunning-Schatz-Elgersma ab initio potential energy surface, the theory predicts that excitation of H2 is 19-68 times more effective than excitation of OH in promoting reaction at 300 K, where the range of values corresponds to different possible assumptions about the quantal effects on reaction-coordinate motion. These values are in much better agreement with the experimental value (about 100) than is a calculation based on the conventional transition state, which yields 2 × 104.",

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T1 - Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(nOH) +H2(nHH)→H2O+H

AU - Truhlar, Donald G.

AU - Isaacson, Alan D.

PY - 1982

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N2 - The state-selected reaction rates OH(nOH = 0,1) + H 2(nHH = 0,1)→H2O + H are calculated by an extension of variational transiton state theory. The reactant vibrational modes are assumed to correlate diabatically with generalized normal modes of a generalized activated complex. Using the Walch-Dunning-Schatz-Elgersma ab initio potential energy surface, the theory predicts that excitation of H2 is 19-68 times more effective than excitation of OH in promoting reaction at 300 K, where the range of values corresponds to different possible assumptions about the quantal effects on reaction-coordinate motion. These values are in much better agreement with the experimental value (about 100) than is a calculation based on the conventional transition state, which yields 2 × 104.

AB - The state-selected reaction rates OH(nOH = 0,1) + H 2(nHH = 0,1)→H2O + H are calculated by an extension of variational transiton state theory. The reactant vibrational modes are assumed to correlate diabatically with generalized normal modes of a generalized activated complex. Using the Walch-Dunning-Schatz-Elgersma ab initio potential energy surface, the theory predicts that excitation of H2 is 19-68 times more effective than excitation of OH in promoting reaction at 300 K, where the range of values corresponds to different possible assumptions about the quantal effects on reaction-coordinate motion. These values are in much better agreement with the experimental value (about 100) than is a calculation based on the conventional transition state, which yields 2 × 104.

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Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(n_OH) +H₂(n_HH)→H₂O+H

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