TY - JOUR

T1 - Rainbows, supernumerary rainbows and interference effects in the angular scattering of chemical reactions: an investigation using Heisenberg’s S matrix programme

AU - Shan, Xiao

AU - Xiahou, Chengkui

AU - Connor, Jonathan

PY - 2017

Y1 - 2017

N2 - In earlier research, we have demonstrated that broad “hidden” rainbows can occur in the product differential cross sections (DCSs) of state-to-state chemical reactions. Here we ask the question: Can pronounced and localized rainbows, rather than broad hidden ones, occur in reactive DCSs? Further motivation comes from recent measurements by H. Pan and K. Liu in, J. Phys. Chem. A, 2016, 120, 6712, of a “bulge” in a reactive DCS, which they conjecture is a rainbow. Our theoretical approach uses a “weak” version of Heisenberg’s scattering matrix program (wHSMP) introduced by X. Shan and J. N. L. Connor, Phys. Chem. Chem. Phys., 2011, 13, 8392. This wHSMP uses four general physical principles for chemical reactions to suggest simple parameterized forms for the S matrix; it does not employ a potential energy surface. We use a parameterization in which the modulus of the S matrix is a smooth-step function of the total angular momentum quantum number, J, and (importantly) its phase is a cubic polynomial in J. We demonstrate for a Legendre partial wave series (PWS) the existence of pronounced rainbows, supernumerary rainbows, and other interference effects, in reactive DCSs. We find that reactive rainbows can be more complicated in their structure than the familiar rainbows of elastic scattering. We also analyse the angular scattering using Nearside-Farside (NF) PWS theory and NF PWS Local Angular Momentum (LAM) theory, including resummations of the PWS. In addition, we apply full and NF asymptotic (semiclassical) rainbow theories to the PWS - in particular, the uniform Airy and transitional Airy approximations for the farside scattering. This lets us prove that structure in the DCSs are indeed rainbows, supernumerary rainbows as well as other interference effects.

AB - In earlier research, we have demonstrated that broad “hidden” rainbows can occur in the product differential cross sections (DCSs) of state-to-state chemical reactions. Here we ask the question: Can pronounced and localized rainbows, rather than broad hidden ones, occur in reactive DCSs? Further motivation comes from recent measurements by H. Pan and K. Liu in, J. Phys. Chem. A, 2016, 120, 6712, of a “bulge” in a reactive DCS, which they conjecture is a rainbow. Our theoretical approach uses a “weak” version of Heisenberg’s scattering matrix program (wHSMP) introduced by X. Shan and J. N. L. Connor, Phys. Chem. Chem. Phys., 2011, 13, 8392. This wHSMP uses four general physical principles for chemical reactions to suggest simple parameterized forms for the S matrix; it does not employ a potential energy surface. We use a parameterization in which the modulus of the S matrix is a smooth-step function of the total angular momentum quantum number, J, and (importantly) its phase is a cubic polynomial in J. We demonstrate for a Legendre partial wave series (PWS) the existence of pronounced rainbows, supernumerary rainbows, and other interference effects, in reactive DCSs. We find that reactive rainbows can be more complicated in their structure than the familiar rainbows of elastic scattering. We also analyse the angular scattering using Nearside-Farside (NF) PWS theory and NF PWS Local Angular Momentum (LAM) theory, including resummations of the PWS. In addition, we apply full and NF asymptotic (semiclassical) rainbow theories to the PWS - in particular, the uniform Airy and transitional Airy approximations for the farside scattering. This lets us prove that structure in the DCSs are indeed rainbows, supernumerary rainbows as well as other interference effects.

U2 - 10.1039/C7CP06654F

DO - 10.1039/C7CP06654F

M3 - Article

SN - 1463-9076

JO - Physical Chemistry: Chemical Physics

JF - Physical Chemistry: Chemical Physics

ER -