The stereodynamics of the two reactions: H + LiH+(v = 0, j = 0) → H2 + Li+ and H+ + LiH(v = 0, j = 0) → H2+ + Li

Abstract

Quasi-classical trajectory (QCT) calculations have been carried out to study the stereodynamics of the reactions H + LiH(+) (v = 0, j = 0) --> H(2) + Li(+) and H(+) + LiH (v = 0, j = 0) --> H(2)(+) + Li which proceed on the two lowest-lying electronic states of the LiH(2)(+) system, using the ab initio potential energy surfaces (PESs) of Martinazzo et al. [J. Chem. Phys., 2003, 119, 11241]. Differential cross sections (DCSs) and alignments of the product rotational angular momentum for the two reactions are reported. Though the two PESs employed in the current calculations have significant differences, the tendencies of the product rotational alignment are same on the whole, and some common features emerge. This interesting phenomenon probably indicates that, for this system, the characters of the PESs have a weak influence on the alignments of the products. The conclusion is confirmed by a further discussion of rotational alignment parameter <P(2) (j' x k)> which also indicates that the two PESs are repulsive, i.e., the exoergic processes of the reactions taking place on the exit valleys of the PESs.

Computing the viscosity of supercooled liquids

“…III is not straightforward in that we have found the evaluation of the A͑ ͒ matrix is sensitive to the sampling robustness of the trajectory; a full discussion of this analysis will be reported in a companion publication. 20 Here Fig. 8͑b͒ shows the calculated values of ͑T͒ down to a temperature where ϳ 10 10 Pa s. The agreement between the Network model and experiments is considered quite satisfactory given the ambiguity in the correspondence between any of the fragile liquids and the BLJ interatomic potential model.…”

“…͑6͒. 20 Since there are no viscosity calculations giving results anywhere near 10 12 Pa s for the BLJ model ͑or any interatomic potential for that matter͒, there is no way to directly validate our value of T g . On the other hand, the mode-coupling theory temperature T c for the BLJ model has been estimated to be T c = 0.435.…”

“…20 We imagine the system is able to sample a number of deep minima within the timescale of the calculation so the average macroscopic properties such as viscosity can take on steady state values. We also assume the activation barriers for hopping are sufficiently high compared to k B T, and the energy dissipation sufficiently efficient that after each hop the system loses memory of its previous history.…”

“…͑6͒. 20 We will test our viscosity formulations in two ways. The first is to compare results with Green-Kubo MD, which is feasible only at low-viscosity values ͑Sec.…”

Vector correlations in the F + HO → HF + O reaction and its isotopic variant

“…For elucidating the stereodynamics of a chemical reaction, QCT is proved to be one of the most popular methods. The QCT code capable of exploring vector properties in a chemical reactive system from Han's group, as well as those from other research groups [13][14][15][16], has been widely employed for the study of chemical reactions [17][18][19][20][21][22][23][24][25][26][27][28]. Both the scalar and vector properties, including product rovibrational distribution, translational distribution, angular distribution, PDDCS (polarization dependant differential cross section), product alignment and orientation parameters can be produced from the corresponding QCT calculations.…”