A QCT study of the cross-section, energy and angular distributions of the OH+D2→HOD+D reaction at ET=0.28 eV on the YZCL2 surface

Classical versus quantum vibrational state distributions for the benchmark polyatomic reaction OH+D2: Checking the validity of the QCT method

“…1), suggesting thereby that the underestimation noted in the introduction is due to the potential energy surface, not to classical mechanics itself. However, it is important to note that this underestimation was also found in previous AQS calculations on the OC surface [5], and in previous QCT calculations in other surfaces, YZCL2 and WSLFH [7]. Moreover, as it was noted previously, in the present work the QCT and QM calculations were performed with J = 0 for a direct comparison between both dynamics methods.…”

“…So, this PES represents an excellent opportunity to test the validity of the QCT method, as compared with AQS and EQS calculations. When in the QCT calculations the standard binning (SB) procedure (which amounts to attribute the same statistical weight to each trajectory) was used, the experimental product vibrational state populations were not reproduced [6][7][8][9]. However, using the Gaussian binning (GB) procedure, which takes into account Bohr quantization principle for vibrational energies [17][18][19][20][21][22][23][24][25][26][27][28], made the expected product state spectrum appear, for the first time as far as polyatomic processes are concerned [10].…”

“…HOD + D is a benchmark polyatomic bimolecular reaction [2][3][4][5][6][7][8][9][10][11]. It is the analogue of F + H 2 ?…”

Ab initio molecular dynamics studies of the OH+D2→HOD+D reaction: Direct classical trajectory calculations by MP2

“…At these energies, the title reaction usually occurs in a direct manner, this is to say, only a moderate amount of vibrational energy is in the transverse modes when the reactive event occur through the transition state. We therefore added only zero-point energy to these modes, and 0.8 kcal mol À1 kinetic energy was added to the reaction coordinate corresponding to the difference between the collision energy in the recent experiments of Davis and coworkers [17] and the most accurate estimated barrier height [19]. The rotation sampling temperature was 300 k. 500 reactive trajectories were obtained using the Hessian based predictor-corrector method [24,28].…”

“…On the other hand, many quasiclassical trajectory calculations(QCT) [18,19] and quantum dynamics studies [20,21] of the title reaction have been carried out, and reaction probabilities, cross sections, rate constants, product energy and angular distribution have been reported for the reaction. The results of these calculations are in good agreement with the experiments [19].…”