Ratios of thermal rate constants calculated with different numbers of single-particle functions. Results relative to a reference 7DH-calculation as specified in Table V: Panel (a) shows the dependence on , , . Panel (b) displays the dependence on , and .
The flux correlation function calculated in the 7DH approximation. Results employing different numbers of Lanczos iterations are displayed.
Ratios of thermal rate constants calculated with different numbers of single-particle functions. Results for different values of , , and relative to results for in the respective coordinate are displayed.
Thermally weighted cumulative reaction probabilities (with a reference temperature ) calculated for PESs using an increasing number of reference points.
Ratios of thermal rate constants calculated for PESs using an increasing number of reference points relative to the result for the MEP-PES.
The flux-flux correlation function: accurate quantum dynamics results for the full PES, the MEP-PES, and approximate 7DH-results for the MEP-PES are displayed.
The cumulative reaction probability : results from accurate quantum dynamics calculations for the full PES (thick solid line) and the MEP-PES (dotted line) are displayed as well as approximate 7DH results for the MEP PES (dashed line). For the full PES, the individual contributions to resulting from the thermal flux eigenstates are also shown (thin solid lines).
Arrhenius plot of the thermal rate constant. Different theoretical (lines) and experimental (symbols) results discussed in the text are presented.
Wave function representation [see Eqs. (6) and (7)].
CCSD(T) energies relative to the reactant asymptote in kcal/mol.
Geometries of the stationary points.
Harmonic frequencies (in ) for the transition state (TS) and the methane reactant (irreducable representation in parenthesis mark degenerate modes).
Single-particle function bases used as references in the convergence tests and finally selected basis set.
Thermal rate constants calculated accurately for the accurate PES and the MEP-PES and results of the (harmonic) transition state theory.
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