Theoretical studies of the reactions H + CH → C + H2 and C + H2 → CH2 using an ab initio global ground-state potential surface for CH2

Lawrence B. Harding, Renee Guadagnini, George C Schatz

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Abstract

Ab initio, multireference, configuration interaction (CI) calculations have been used to characterize the groundstate potential surface of methylene. The calculations employ a full-valence, complete-active-space reference wave function and a (4s,3p,2d,1f/3s,2p,1d) basis set. The calculations were carried out at ∼6000 points, and the resulting energies were fit to a many-body expansion including conical intersections between the 3B1 and 3A2 states for C2v geometries and between the 3II and 3Σ- states for linear geometries. The calculations show that the C2v conical intersection provides a zero barrier route for the C(3P) + H2 insertion reaction. Quasiclassical trajectory studies of the title reactions using the global surface indicate that both reactions proceed without activation energy and that the thermal rate constants are nearly independent of temperature. The rate constants for H + CH agree with high-temperature (2000 K) experimental studies but are substantially higher (factor of 10) than a measurement at 297 K. For C + H2, the CH2 lifetimes at thermal energies are approximately 20 ps which is in agreement with an experimentally derived estimate.

Original languageEnglish
Pages (from-to)5472-5481
Number of pages10
JournalJournal of Physical Chemistry
Volume97
Issue number21
Publication statusPublished - 1993

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Surface potential
Ground state
methylidyne
ground state
intersections
Rate constants
Geometry
Wave functions
geometry
Thermal energy
thermal energy
methylene
configuration interaction
insertion
Activation energy
routes
Trajectories
trajectories
wave functions
activation energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Theoretical studies of the reactions H + CH → C + H2 and C + H2 → CH2 using an ab initio global ground-state potential surface for CH2. / Harding, Lawrence B.; Guadagnini, Renee; Schatz, George C.

In: Journal of Physical Chemistry, Vol. 97, No. 21, 1993, p. 5472-5481.

Research output: Contribution to journalArticle

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AB - Ab initio, multireference, configuration interaction (CI) calculations have been used to characterize the groundstate potential surface of methylene. The calculations employ a full-valence, complete-active-space reference wave function and a (4s,3p,2d,1f/3s,2p,1d) basis set. The calculations were carried out at ∼6000 points, and the resulting energies were fit to a many-body expansion including conical intersections between the 3B1 and 3A2 states for C2v geometries and between the 3II and 3Σ- states for linear geometries. The calculations show that the C2v conical intersection provides a zero barrier route for the C(3P) + H2 insertion reaction. Quasiclassical trajectory studies of the title reactions using the global surface indicate that both reactions proceed without activation energy and that the thermal rate constants are nearly independent of temperature. The rate constants for H + CH agree with high-temperature (2000 K) experimental studies but are substantially higher (factor of 10) than a measurement at 297 K. For C + H2, the CH2 lifetimes at thermal energies are approximately 20 ps which is in agreement with an experimentally derived estimate.

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