Rigorous quantum calculations for atom-molecule chemical reactions in electric fields: from single to multiple partial wave regimes

Abstract

We present an efficient method for rigorous quantum calculations of cross sections for atom-molecule reactive scattering in the presence of a dc electric field. The wavefunction of the reaction complex is expanded in an overcomplete set of arrangement-dependent Fock-Delves hyperspherical basis functions and the interactions of the reactants and products with electric fields are accounted for in the total angular momentum representation. A significant computational challenge affecting our previously developed approach [Phys. Rev. Lett. $115$, 023201 (2015)] is addressed by an efficient asymptotic frame transformation between the hyperspherical and Jacobi coordinates in the presence of an external field. Using accurate {\it ab initio} potential energy surfaces, we calculate total and state-resolved cross sections for the chemical reactions LiF$(v=1,j=0)$ + H $\to$ Li + HF($v^{\prime }=0,j^{\prime }$) and F + HD$(v=0,j=0)$ $\to$ HF + D, DF + H as functions of collision energy and electric field strength. The field dependence of the cross sections for the LiF + H chemical reaction exhibits resonance structure mediated by tunneling-driven interactions between reactants and products. No significant field effects are found for the F + HD $\to$ HF + D, DF + H chemical reaction at 1 Kelvin, even for state-resolved transitions and with field magnitudes reaching 200 kV/cm. Our calculations illustrate the essential role of basis set convergence for the proper interpretation of external field effects on chemical reaction dynamics. While reduced-basis calculations for the F + HD reaction indicate significant effects of electric fields on product state distributions, these effects vanish when the number of total angular momentum basis states is increased.

References in corpus (58)

• Cold and Ultracold Molecules: Science, Technology, and Applications
• Cold molecules: Progress in Quantum Engineering of Chemistry and Quantum Matter
• Magneto-optical trapping of a diatomic molecule
• Molecules cooled below the Doppler limit
• Molecules Near Absolute Zero and External Field Control of Atomic and Molecular Dynamics
• Sisyphus Laser Cooling of a Polyatomic Molecule
• Cold hybrid ion-atom systems
• Laser Cooling of Optically Trapped Molecules
• Universal rate constants for reactive collisions of ultracold molecules
• Sisyphus Cooling of Electrically Trapped Polyatomic Molecules
• Direct Laser Cooling of a Symmetric Top Molecule
• Optoelectrical cooling of polar molecules to sub-millikelvin temperatures
• Observation of magnetically tunable Feshbach resonances in ultracold ${}^{23}$Na${}^{40}$K+${}^{40}$K collisions
• Observation of Bose-Einstein Condensation of Dipolar Molecules
• Imaging resonances in low-energy NO-He inelastic collisions
• Statistical Aspects of Ultracold Resonant Scattering
• Microwave shielding of ultracold polar molecules
• Direct probe of anisotropy in atom-molecule collisions via quantum scattering resonances
• Resonant collisional shielding of reactive molecules using electric fields
• Repulsive shield between polar molecules
• Controlling electronic spin relaxation of cold molecules with electric fields
• Controlling the scattering length of ultracold dipolar molecules
• Quantum state manipulation and cooling of ultracold molecules
• Imaging the onset of the resonance regime in low-energy NO-He collisions
• Bimolecular chemistry in the ultracold regime
• Magnetic Trapping of Cold Methyl Radicals
• Quantum Control of Trapped Polyatomic Molecules for eEDM Searches
• Field-linked resonances of polar molecules
• A Feshbach resonance in collisions between ultracold ground state molecules
• Ultracold spin-polarized mixtures of 2Sigma molecules with S-state atoms: Collisional stability and implications for sympathetic cooling
• Direct laser cooling of calcium monohydride molecules
• Quantum theory of chemical reactions in the presence of electromagnetic fields
• Blue-Detuned Magneto-Optical Trap of Molecules
• Quantum dynamics of the Li+HF-->H+LiF reaction at ultralow temperatures
• Magnetic Feshbach resonances in collisions of ${}^{23}$Na${}^{40}$K with ${}^{40}$K
• Tuning bimolecular chemical reactions by electric fields
• Cold trapped molecular ions and hybrid platforms for ions and neutral particles
• Tomography of Feshbach Resonance States
• Quantum state resolved molecular dipolar collisions over four decades of energy
• Complete quantum coherent control of ultracold molecular collisions
• Atom-molecule collisions, spin relaxation, and sympathetic cooling in an ultracold spin-polarized Rb(${}^2\mathrm{S}$)-SrF${(}^2{\Sigma }^{+})$ mixture
• Phase-locking between different partial-waves in atom-ion spin-exchange collisions
• Efficient method for quantum calculations of molecule - molecule scattering properties in a magnetic field
• Universal probability distributions of scattering observables in ultracold molecular collisions
• Signature of the $s$-wave regime high above ultralow temperatures
• Spectrum of Feshbach resonances in NaLi $+$ Na collisions
• Hyperfine-to-rotational energy transfer in ultracold atom-molecule collisions
• The excitation function for Li+HF-->LiF+H at collision energies below 80 meV
• Total angular momentum representation for atom-molecule collisions in electric fields
• Ab initio calculation of the spectrum of Feshbach resonances in NaLi + Na collisions
• Coherent control of reactive scattering at low temperatures: Signatures of quantum interference in the differential cross sections for F + H2 and F + HD
• Signatures of Non-universal Quantum Dynamics of Ultracold Chemical Reactions of Polar Alkali-dimer Molecules with Alkali-metal Atoms: Li(${}^2$S) +NaLi($a^3{\Sigma }^{+}$) $\to$ Na(${}^2$S) + Li${}_2$($a^3{\Sigma }_u^{+}$)
• Full-dimensional quantum scattering calculations on ultracold atom-molecule collisions in magnetic fields: The role of molecular vibrations
• Hyperfine dependent atom-molecule loss analyzed by the analytic solution of few-body loss equations
• Observation of the P-wave Shape Resonance
• Magnetic Feshbach resonances in ultracold atom-molecule collisions
• Quantum control of ion-atom collisions beyond the ultracold regime
• Feshbach Resonances in Cold Collisions: Benchmarking State of the Art ab initio Potential Energy Surfaces