Parametrized direct dynamics study of rate constants of h with CH4 from 250 to 2400 K

Four implicit potential energy surfaces (PESs) with specific-reaction-parameters (SRP) are developed and tested for the reaction CH4+H→CH3+H2. The first is called MPW60 and is based on the modified Perdew–Wang hybrid density-functional method with the percentage of the Hartree–Fock exchange equal to 60%. The other three PESs are constructed with multi-coefficient correlation methods (MCCMs). The second is called MCOMP2-SRP, and the third is called MC-QCISD-SRP. Both of them are parametrized for this specific reaction by starting with their corresponding global parameters. The fourth is called MCG3-SRP and is based on the MCG3-CHO semiglobal parametrization with further refinement for this specific reaction. All four SRP surfaces have a classical forward barrier height of 14.8 kcal/mol, and all three MCCM SRP surfaces have a classical endoergicity of 3.3 kcal/mol. The stationary point geometries, vibrational frequencies, and zero-point-energies are reported for several standard single-level methods and MCC...

[1]  M. Su,et al.  Rate constants for H + CH4, CH3 + H2, and CH4 dissociation at high temperature , 2001 .

[2]  Donald G. Truhlar,et al.  Test of variational transition state theory with multidimensional tunneling contributions against an accurate full-dimensional rate constant calculation for a six-atom system , 2001 .

[3]  Joel M. Bowman,et al.  The importance of an accurate CH4 vibrational partition function in full dimensionality calculations of the H+CH4→H2+CH3 reaction , 2001 .

[4]  D. Truhlar,et al.  Multi-coefficient Correlation Method: Comparison of Specific-Range Reaction Parameters to General Parameters for CnHxOy Compounds , 2001 .

[5]  Donald G. Truhlar,et al.  How Well Can Hybrid Density Functional Methods Predict Transition State Geometries and Barrier Heights , 2001 .

[6]  I. R. Slagle,et al.  Kinetics of Reactions of H Atoms With Methane and Chlorinated Methanes , 2001 .

[7]  Hua-Gen Yu,et al.  Quantum dynamics of the reaction of hydrogen atom with methane , 2000 .

[8]  Uwe Manthe,et al.  Full dimensional quantum calculations of the CH4+H→CH3+H2 reaction rate , 2000 .

[9]  Donald G. Truhlar,et al.  MC-QCISD: Multi-coefficient correlation method based on quadratic configuration interaction with single and double excitations , 2000 .

[10]  Donald G. Truhlar,et al.  Adiabatic connection for kinetics , 2000 .

[11]  D. Truhlar,et al.  Multilevel geometry optimization , 2000 .

[12]  G. Nyman,et al.  Four-dimensional quantum scattering calculations on the H+CH4→H2+CH3 reaction , 1999 .

[13]  D. Truhlar,et al.  MULTI-COEFFICIENT CORRELATION METHOD FOR QUANTUM CHEMISTRY , 1999 .

[14]  D. Truhlar,et al.  Multi-coefficient Gaussian-3 method for calculating potential energy surfaces , 1999 .

[15]  T. Takayanagi,et al.  Theoretical study of an isotope effect on rate constants for the CH3+H2→CH4+H and CD3+H2→CD3H+H reactions using variational transition state theory and the multidimensional semiclassical tunneling method , 1999 .

[16]  Donald G. Truhlar,et al.  Optimized Parameters for Scaling Correlation Energy , 1999 .

[17]  D. Truhlar,et al.  The calculation of kinetic isotope effects based on a single reaction path , 1998 .

[18]  Vincenzo Barone,et al.  Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models , 1998 .

[19]  J. Bertrán,et al.  Variational transition state theory and tunneling calculations with reorientation of the generalized transition states for methyl cation transfer , 1998 .

[20]  Stanislav I. Stoliarov,et al.  Kinetics of the C2H3 + H2 ⇄ H + C2H4 and CH3 + H2 ⇄ H + CH4 Reactions , 1996 .

[21]  T. Bérces.  The reaction path in chemistry: current approaches and perspectives , 1996 .

[22]  T. Takayanagi.  Reduced dimensionality calculations of quantum reactive scattering for the H+CH4→H2+CH3 reaction , 1996 .

[23]  K. S. Shin,et al.  Shock Tube Study of the Reaction between CH3 and H2 , 1995 .

[24]  Robert G. Gilbert,et al.  Classical trajectory studies of the reaction CH4+H→CH3+H2 , 1995 .

[25]  D. Truhlar,et al.  Reaction‐path potential and vibrational frequencies in terms of curvilinear internal coordinates , 1995 .

[26]  Thanh N. Truong,et al.  A new direct ab initio dynamics method for calculating thermal rate constants from density functional theory , 1994 .

[27]  T. Truong.  A direct ab initio dynamics approach for calculating thermal rate constants using variational transition state theory and multidimensional semiclassical tunneling methods. An application to the CH4+H↔CH3+H2 reaction , 1994 .

[28]  P. Pacey,et al.  ELECTRON SPIN RESONANCE STUDY OF THE REACTION OF HYDROGEN ATOMS WITH METHANE , 1994 .

[29]  J. Gauss,et al.  Accurate coupled cluster reaction enthalpies and activation energies for X+H2→XH+H (X=F, OH, NH2, and CH3) , 1993 .

[30]  Donald G. Truhlar,et al.  Molecular modeling of the kinetic isotope effect for the [1,5]-sigmatropic rearrangement of cis-1,3-pentadiene , 1993 .

[31]  Jan M. L. Martin.  On the performance of large Gaussian basis sets for the computation of total atomization energies , 1992 .

[32]  Benny G. Johnson,et al.  An investigation of the performance of a hybrid of Hartree‐Fock and density functional theory , 1992 .

[33]  P. Patterson,et al.  Direct rate constant measurements for atomic hydrogen + methane .fwdarw. methyl + hydrogen, 897-1729 K, using the flash photolysis-shock tube technique , 1991 .

[34]  Warren J. Hehre,et al.  AB INITIO Molecular Orbital Theory , 1986 .

[35]  D. L. Gray,et al.  The anharmonic force field and equilibrium structure of methane , 1979 .

[36]  Donald G. Truhlar,et al.  Criterion of minimum state density in the transition state theory of bimolecular reactions , 1979 .

[37]  D. Truhlar,et al.  Reaction-Path Dynamics in Redundant Internal Coordinates , 1998 .

[38]  D. C. Clary,et al.  The Theory of Chemical Reaction Dynamics , 1986 .

[39]  Michael Baer,et al.  Theory of chemical reaction dynamics , 1985 .

[40]  B. C. Garrett,et al.  Incorporation of quantum effects in generalized-transition-state theory , 1982 .