Angular momentum disposal in atom exchange reactions

Abstract

For an A + BC -+ AB+C reaction, the partitioning of the total angular momentum J between initial and final orbital momenta of the collision partners, 1 and l', and rotation of the reactant and product molecules, j and j ' , often imposes distinctive dynamical features. Many examples are known that approach one or another of two very different limiting cases: ( I ) J = 1 = j ' or (11) J = I = 1'. In a quasiclassical trajectory study of the H + Li2 -+ LiH + Li reaction, we find the distributions of the product scattering angle and the rotational orientation of j ' relative to the initial velocity conform to case 11. However, the dihedral orientation of j ' relative to the plane of initial and final velocity vectors conforms to case I. Also, the opacity function has an unusual bimodal form and the entropy deficiency for the triple-angle correlation is extremely large. The cu1prit.k vector addition: both j ' and I' are large and largely opposed, so the reaction appears schizophrenic.

Product rotational polarization: Stereodynamics of the reaction Cl(2P3/2)+CD4(v=0,j=0)→DCl(v′=0,j′=1)+CD3

“…The dihedral angle distribution P( r ) is in good accordance with the results obtained by Herschbach and co-workers 7 that the distribution of JЈ does not have azimuthal symmetry about the initial relative velocity vector for the CsϩCH 3 I reaction. We note in passing that the HϩLi 2 reaction, studied by Herschbach and co-workers, 5 proceeds via statistical long-lived complexes, in contrast to the ClϩCD 4 system studied here. However, in common with the HϩLi 2 study, the results reveal that the distribution of dihedral angles, P( r ), is a crucially sensitive indicator of the stereodynamics of the ClϩCD 4 reaction.…”

“…Since the pioneering work of Fano and Macek 1 and of Herschbach and co-workers, [2][3][4][5][6][7] it has been recognized that a detailed, three-dimensional picture of the dynamics of reactive collisions emerges with the determination of the correlated angular distribution describing the mutual orientations of the reagent and product linear and angular momentum. Experimental and theoretical interest in vector correlations in the reaction processes…”

Stereo‐dynamics of the F + HCl → HF + Cl reaction

“…HF þ Cl reaction have focused exclusively on the scalar property. To comprehend the dynamics of the F þ HCl reaction fully, it is quite necessary to study their vector properties, which can provide the valuable information about chemical reaction stereo-dynamics [21][22][23][24][25][26][27]. In this work, we will carry out the QCT calculations on the DHSN-PES [15] for the title reaction and investigate its vector properties.…”

Theoretical study of the stereodynamics of the reactions of D−+H2→H−+HD and H−+D2→D−+HD

“…In order to understand the dynamics of the H À + D 2 reaction and D À + H 2 reaction fully, it is important to study not only their scalar properties, but also their vector properties. The vector properties of chemical reaction can provide the valuable information about chemical reaction stereodynamics [24][25][26][27]. Vectors properties, such as velocities and angular momentum, possess not only magnitudes that can be directly related to translational and rotational energies, but also well-defined directions.…”