Time-dependent quantum mechanical calculations on H + O2 for total angular momentum J &gt; 0: Comparing different dynamical approximations

State-to-state reactive differential cross sections for the H + H 2 → H 2 + H reaction on five different potential energy surfaces employing a new quantum wavepacket computer code: DIFFREALWAVE J. Chem. Phys. 125, 164303 (2006) The quantum wavepacket parallel computational code DIFFREALWAVE is used to calculate state-to-state integral and differential cross sections for the title reaction on the BKMP2 surface in the total energy range of 0.4-1.2 eV with D 2 initially in its ground vibrational-rotational state. The role of Coriolis couplings in the state-to-state quantum calculations is examined in detail.Comparison of the results from calculations including the full Coriolis coupling and those using the centrifugal sudden approximation demonstrates that both the energy dependence and the angular dependence of the calculated cross sections are extremely sensitive to the Coriolis coupling, thus emphasizing the importance of including it correctly in an accurate state-to-state calculation.

Section: Discussionsupporting

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Coriolis coupling effects in the calculation of state-to-state integral and differential cross sections for the H+D2 reaction

Chu

Han

Hankel

et al. 2007

“…Quantum calculation of reactions proceeding without a potential barrier, and typically by complex formation, are very demanding, due both to the presence of a complex region, which causes the wave function oscillate rapidly, and also to the large region of configuration space that is accessible to the reaction. Previous, full dimensionality quantum calculations of such reactions have been reported for HϩO 2 , [22][23][24][25] 26,27 NϩH 2 , 28 and the ion-molecule reaction N ϩ ϩH 2 , 29 Ne ϩH 2 ϩ , 30 H ϩ ϩH 2 , 31,32 and He ϩ ϩH 2 . 33 So this O( 1 D) ϩHBr reaction is especially demanding, and also interesting due to the presence of two products channels.…”

Section: Introductionmentioning

confidence: 99%

Quantum scattering calculation of the O(1D)+HBr reaction

Tang

Chen

et al. 2004

Three-dimensional time-dependent quantum wave packet calculation for the O( 1 D)ϩHBr reaction has been carried out using an accurate ab initio global potential energy surface ͓K. A. Peterson, J. Chem. Phys. 113, 4598 ͑2000͔͒. The calculations show that the initial state-selected reaction probabilities are dominated by resonance structures, and the lifetime of the resonance is generally in the subpicosecond time scale. The energy dependence of the reaction cross section is computed, which manifests still resonance structures, and is a decreasing function of the translational energy. The thermal rate constants are also computed, which are nearly independent on the temperature. The calculation results are discussed and compared to similar reaction with deep well.

“…This observation is consistent with the previously reported JϾ0 total reaction probability calculations for this system, which show that for HO 2 the Coriolis coupling is important and cannot be ignored. 58 Interestingly, this situation is in contrast to the H 2 O and HOCl systems, for which HC or AR is a good approximation.…”

Section: B Bound and Resonance Energies "Rates…mentioning

confidence: 80%

Converged quantum calculations of HO2 bound states and resonances for J=6 and 10

Zhang

Smith

2004

Accurate quantum calculation of the bound and resonant rovibrational states of Li − ( H 2 ) J. Chem. Phys. 122, 124318 (2005) Bound and resonance states of HO 2 are calculated quantum mechanically using both the Lanczos homogeneous filter diagonalization method and the real Chebyshev filter diagonalization method for nonzero total angular momentum Jϭ6 and 10, using a parallel computing strategy. For bound states, agreement between the two methods is quite satisfactory; for resonances, while the energies are in good agreement, the widths are in general agreement. The quantum nonzero-J specific unimolecular dissociation rates for HO 2 are also calculated.