RRKM CALCULATION : DECOMPOSITION OF METHANOL TO CH3 + OH LATEST UPDATE August 1994 NUMBER OF TERMS IN INTEGRATION 400 ENERGY SPACING (CM-1) 100 NUMBER OF INPUT PRESSURES: 1 NUMBER OF INPUT TEMPERATURES: 1 NUMBER OF CHANNELS: 1 FOR CHANNEL NUMBER 1: SINUSOIDALLY HINDERED NEUTRAL-NEUTRAL REACTION ROTATIONAL ENERGY GRAINSIZE: 100.0000 CONVERGENCE PARAMETER: 0.0025 CHANNEL NUMBER 1 HAS 2 SINUSOIDALLY HINDERED ROTORS CALCULATIONS USE ANGULAR MOMENTUM-CONSERVING TREATMENT: FULL K(E,J); WITH STRONG COLLISIONS FOR ROTATIONAL RELAXATION. FOR J-CONSERVING TREATMENT: R DAGGER (ANGSTROM) R EQUILIBRIUM (ANGSTROM) CHANNEL 3.500 1.421 1 FOR CHANNEL NUMBER 1: NUMBER OF INPUT MORSE POTENTIAL POINTS = 1 DISTANCE (ANGSTROM) POTENTIAL (KCAL MOL-1) 4.300 89.790 MOLECULE COMPLEX(ES) 1 CRITICAL ENERGY(KCAL/MOL) 90.360 (KJ/MOL) 378.066 EXTERNAL SYMMETRY NUMBERS 1.000 1.000 COLLISION DIAMETER (ANGSTROM) 3.58 WEIGHT OF REACTANT (A.M.U.) 32.04 WEIGHT OF BATH GAS (A.M.U.) 39.95 LENNARD JONES COLLISION FREQUENCY USED WELL DEPTH = 227.0 K (KJ/MOL) 378.066 OVERALL ROTATION: B (CM-1) 8.20E-01 1.63E-01 CORRESPONDING MOMENTS OF INERTIA (AMU A**2) 20.546 103.614 DIMENSIONS OF ADIABATIC ROTATIONS 2 2 EXTERNAL (2-DIMENSIONAL) ROTATION TREATED AS ADIABATIC. 1-DIMENSIONAL EXTERNAL ROTOR ABOUT UNIQUE AXIS TREATED AS FULLY ACTIVE. NO. OF FREQUENCIES 11 5 FREQUENCIES AND DEGENERACIES 3681 1 3735 1 3000 1 3184 2 2960 1 3002 1 2844 1 1383 2 1477 2 580 1 1455 1 0 0 1345 1 0 0 1165 1 0 0 1060 1 0 0 1033 1 0 0 295 1 0 0 FREE INTERNAL ROTATIONS: B SYMMETRY DIMEN- B SYMMETRY DIMEN- (CM-1) NO. SION (CM-1) NO. SION 4.17E+00 1.000 1 4.79E+00 3.000 1 0.00E+00 0.000 0 9.57E+00 2.000 2 0.00E+00 0.000 0 1.77E+01 1.000 2 BETA VALUE OBTAINED FROM MORSE FITTING: FOR CHANNEL 1 BETA = 2.0250 FOR HINDERED ROTOR TREATMENT: FOR CHANNEL 1 V0 = 932.2179 CM-1 1 DECOMPOSITION OF METHANOL TO CH3 + OH TEMPERATURE 1000.0 KELVIN CHANNEL(S) 1 CRITICAL ENERGIES (KCAL/MOL) 90.36 HIGH PRESSURE RATE COEFFICIENT (FROM NUMERICAL INTEGRATION) (S-1) 3.62E-04 HIGH PRESSURE RATE COEFFICIENT USING /I FACTOR (CALCULATED NUMERICALLY) (S-1) = 1.62E-04 (CHANNEL 1) HIGH PRESSURE /I FACTOR = 8.49 WARNING : THE TWO HIGH PRESSURE RATES FOR CHANNEL 1 DIFFER BY MORE THAN 20% MOVE THIS TRANSITION STATE TO OBTAIN A BETTER AGREEMENT. RATIO OF NUMERICAL TO EXACT PARTITION FUNCTION = 0.818 CORRECTED HIGH PRESSURE RATE: 2.96E-04 THERMODYNAMICS MOLECULE COMPLEX(ES):1 VIBRATION ENTROPY (J/MOL K) 48.40 19.54 ROTATION ENTROPY (J/MOL K) 94.55 174.10 (INTERNAL AND EXTERNAL ROTATIONS INCLUDED TOGETHER) TRANSLATIONAL ENTROPY (J/MOL K) 177.14 177.14 TOTAL ENTROPY (J/MOL K) 320.10 370.78 APPROX. LOG A FROM THERMODYNAMICS 16.400 VIB. PARTITION FUNCTION 1.06E+01 2.46E+00 ROTNL PARTITION FUNCTION 1.94E+04 1.31E+07 (INTERNAL AND EXTERNAL ROTATIONS INCLUDED TOGETHER) CHANNEL(S) 1 APPROX. HIGH PRES. ACTVN. ENERGY (KCAL/MOL) 91.19 STRONG COLLISION CALCULATION: PRESSURE OMEGA K1 K1/K1 INF K2 K2/K2 INF (TORR) (S-1) (S-1) 1.00E+02 4.25E+08 7.40E-05 2.50E-01 TOTAL STRONG COLLISION (E,J) LOW PRESSURE RATE COEFFICIENT (CM3 MOL-1 S-1) 3.78E+02 STRONG COLLISION (E,J=0) LOW PRESSURE RATE COEFFICIENT (CM3 MOL-1 S-1) 1.03E+02