Quantum mechanics and quasiclassical study of the H/D+FO → OH/OD+F, HF/DF+O reactions: Chemical stereodynamics

Abstract

The time-dependent quantum wave packet and the quasi-classical trajectory (QCT) calculations for the title reactions are carried out using three recent-developed accurate potential energy surfaces of the 1(1)A', 1(3)A', and 1(3)A'' states. The two commonly used polarization-dependent differential cross sections, dsigma(00)/domega(t), dsigma(20)/domega(t), with omega(t) being the polar coordinates of the product velocity omega', and the three angular distributions, P(theta(r)), P(Phi(r)), and P(theta(r),Phi(r)), with theta(r), Phi(r) being the polar angles of the product angular momentum, are generated in the center-of-mass frame using the QCT method to gain insight into the alignment and the orientation of the product molecules. Influences of the potential energy surface, the collision energy, and the isotope mass on the stereodynamics are shown and discussed. Validity of the QCT calculation has been examined and proved in the comparison with the quantum wave packet calculation.

Stereodynamics investigation of F + HO → HF + O(1D) on the ground singlet potential energy surface by means of the quasi-classical trajectory method

“…The elucidation of the QCT method has been reported in previous studies. 14,[18][19][20][21][22][23][24][25][26][27][28][29][30][31][32] Hence, the specification is not illustrated and only the most important details are described here. The QCT calculation was performed on the ground one 1 A= state of the F + HO ¡ HF + O( 1 D) reaction.…”

“…[8][9][10] These PESs have been widely used in QCT and quantum mechanical scattering calculations. [11][12][13][14][15][16][17] There are a great number of theoretical studies on the HOF reactive system on different PESs. However, most researchers only have investigated the reactions occurring on the triplet state.…”

Time-Dependent Wave Packet Quantum Scattering and Quasi-Classical Trajectory Calculations of the H + FCl(v=0,j=0) → HF + Cl/HCl + F Reaction

“…It is worth noting that the Jacobi angle θ is used in the above calculation to distinguish between the two product channels with 0° ≤ θ ≤ 90° and 90° < θ ≤ 180°, respectively. More details of the methodology and parameters can be found elsewhere. − In order to get the converged results, many test calculations on each parameter have been done. Table lists the parameters used in present quantum scattering calculations.…”

Wave packet calculations on nonadiabatic effects for the O(3P)+HF(1Σ+) reaction under hyperthermal conditions

“…In the last few years, global accurate three-dimensional adiabatic potential energy surfaces (PES's) have been obtained for all the triplet 13, 14 and singlet 15 electronic states connecting the O( 3 P, 1 D)+HF asymptotes. On these potential energy surfaces, both reactivity 13,14,[16][17][18][19][20][21][22] and spectroscopy 15, 23-25 of the OHF system have been extensively studied. Note that, due to the large endoergicity of the O( 3 P)+HF→F( 2 P)+OH( 2 ) reaction, the only studies carried out up to date on the triplet lowest-lying surfaces were performed for the reverse F( 2 P)+OH→O( 3 P)+HF reaction.…”

“…Also, the dynamics of the FO( 2 )+H→OH( 2 )+F( 2 P) reaction on the ground triplet state (1 3 A ) has been recently analyzed by means of both QCT 19,20 and quantum mechanical wave packet calculations. 18,19 Chu et al 19,21 have also focused on the OH( 2 )+F( 2 P) and O( 1 D)+HF channels, on the triplets (1 3 A and 1 3 A ) and singlet ( 1 A ) states, respectively. Later, a model of coupled diabatic PES's for the three lowest triplet electronic states has been also proposed, 26 what allows to study the influence of the nonadiabatic mechanisms on the dynamics of the system, mainly applied to the study of the photodetachment spectrum of the OHF − anion.…”