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SEMI-CLASSICAL TRANSITION STATE THEORY APPLIED TO MULTIWELL CALCULATIONS ON THE OH+CO →H+CO 2 REACTION

SEMI-CLASSICAL TRANSITION STATE THEORY APPLIED TO MULTIWELL CALCULATIONS ON THE OH+CO →H+CO 2 REACTION Ralph E. Weston Jr. a , Thanh Lam Nguyen b , John F. Stanton c , and John R. Barker b a Chemistry Department, Brookhaven National Laboratory, Upton, NY

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SEMI-CLASSICAL TRANSITION STATE THEORY APPLIED TO MULTIWELL CALCULATIONS ON THE OH+CO →H+CO 2 REACTION

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  1. SEMI-CLASSICAL TRANSITION STATE THEORY APPLIED TO MULTIWELL CALCULATIONS ON THE OH+CO →H+CO2 REACTION Ralph E. Weston Jr.a, Thanh Lam Nguyenb, John F. Stantonc, and John R. Barkerb a Chemistry Department, Brookhaven National Laboratory, Upton, NY b Department of Atmospheric, Ocean and Space Sciences, University of Michigan, Ann Arbor,MI c Department of Chemistry and Biochemistry, University of Texas, Austin, TX

  2. ■ Ab initio calculations ■ SCTST calculations of rate constants ■ Multiwell solutions of Master Equation ■ Results and Discussion ■ Conclusions

  3. Ab initio calculations Energies: CCSD(T) method extrapolated to complete basis set CCSD(T)/CBS(aVDZ,aVTZ,aVQZ) (∓ 0.5 kcal) Dunning, 1999 Geometries and harmonic frequencies: CCSD(T,full)/aug-cc-pVTZ Anharmonic constants: CCSD(T)/ANO CFOUR program (Stanton,2009)

  4. Local potential energy surface

  5. SCTST calculations Miller (1975, 1990) Nguyen, Stanton, Barker (2010) ZPE’s include harmonic frequencies, anharmonic constants, G0 (involving normal coordinate f.c.), SO correction DBOC was NOT included; may be important in OD isotope effect

  6. SCTST calculation of k(E) SCTST method has previously been applied to calculate canonical rate constants k(T) In this application it is use to obtain micro- canonical rate constants k(E) for use in master equation calculations

  7. Multiwell calculations Barker, et al. Stochastic method dX/dt = rates of formation and removal+energy transfer P(E,E’) = N exp [-(E-E’)/α] α = 100—200 cm-1

  8. Conclusions This is work in progress: how far must we go in choosing basis functions for a priori calculations? Even with a large basis set, a priori calculations are not in close agreement with experimental results Ad hoc adjustment of barrier heights gives results in good agreement with experiment at T = 98-819K and P up to ~1000 bar

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