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Optical pumping of molecules provides unique opportunities for control of chemical reactions at a wide range of rotational energies. This work reports a chemical reaction with extreme rotational excitation of a reactant and its kinetic characterization. We investigate the chemical reactivity for the hydrogen abstraction reaction SiO⁺+ H₂ → SiOH⁺+ H in an ion trap. The SiO⁺cations are prepared in a narrow rotational state distribution, including super-rotor states with rotational quantum number (j) as high as 170, using a broad-band optical pumping method. We show that the super-rotor states of SiO⁺substantially enhance the reaction rate, a trend reproduced by complementary theoretical studies. We reveal the mechanism for the rotational enhancement of the reactivity to be a strong coupling of the SiO⁺rotational mode with the reaction coordinate at the transition state on the dominant dynamical pathway.

 

The calcium monofluoride (CaF) molecule has emerged as a promising candidate for precision measurements, quantum simulation, and ultracold chemistry experiments. Inelastic and reactive collisions of laser cooled CaF molecules in optical tweezers have recently been reported and collisions of cold Li atoms with CaF are of current experimental interest. In this paper, we report ab initio electronic structure and full-dimensional quantum dynamical calculations of the Li + CaF → LiF + Ca chemical reaction. The electronic structure calculations are performed using the internally contracted multi-reference configuration-interaction method with Davidson correction (MRCI + Q). An analytic fit of the interaction energies is obtained using a many-body expansion method. A coupled-channel quantum reactive scattering approach implemented in hyperspherical coordinates is adopted for the scattering calculations under cold conditions. Results show that the Li + CaF reaction populates several low-lying vibrational levels and many rotational levels of the product LiF molecule and that the reaction is inefficient in the 1–100 mK regime allowing sympathetic cooling of CaF by collisions with cold Li atoms. 

Bismuth ferrite has garnered considerable attention as a promising candidate for magnetoelectric spin-orbit coupled logic-in-memory. As model systems, epitaxial BiFeO₃thin films have typically been deposited at relatively high temperatures (650–800 °C), higher than allowed for direct integration with silicon-CMOS platforms. Here, we circumvent this problem by growing lanthanum-substituted BiFeO₃at 450 °C (which is reasonably compatible with silicon-CMOS integration) on epitaxial BaPb_0.75Bi_0.25O₃electrodes. Notwithstanding the large lattice mismatch between the La-BiFeO₃, BaPb_0.75Bi_0.25O₃, and SrTiO₃(001) substrates, all the layers in the heterostructures are well ordered with a [001] texture. Polarization mapping using atomic resolution STEM imaging and vector mapping established the short-range polarization ordering in the low temperature grown La-BiFeO₃. Current-voltage, pulsed-switching, fatigue, and retention measurements follow the characteristic behavior of high-temperature grown La-BiFeO₃, where SrRuO₃typically serves as the metallic electrode. These results provide a possible route for realizing epitaxial multiferroics on complex-oxide buffer layers at low temperatures and opens the door for potential silicon-CMOS integration.

 

The formation of two-electron chemical bonds requires the alignment of spins. Hence, it is well established for gas-phase reactions that changing a molecule’s electronic spin state can dramatically alter its reactivity. For reactions occurring at surfaces, which are of great interest during, among other processes, heterogeneous catalysis, there is an absence of definitive state-to-state experiments capable of observing spin conservation and therefore the role of electronic spin in surface chemistry remains controversial. Here we use an incoming/outgoing correlation ion imaging technique to perform scattering experiments for O(³P) and O(¹D) atoms colliding with a graphite surface, in which the initial spin-state distribution is controlled and the final spin states determined. We demonstrate that O(¹D) is more reactive with graphite than O(³P). We also identify electronically nonadiabatic pathways whereby incident O(¹D) is quenched to O(³P), which departs from the surface. With the help of molecular dynamics simulations carried out on high-dimensional machine-learning-assisted first-principles potential energy surfaces, we obtain a mechanistic understanding for this system: spin-forbidden transitions do occur, but with low probabilities.

 

Abstract The Born–Oppenheimer approximation is the keystone of modern computational chemistry and there is wide interest in understanding under what conditions it remains valid. Hydrogen atom scattering from insulator, semi-metal and metal surfaces has helped provide such information. The approximation is adequate for insulators and for metals it fails, but not severely. Here we present hydrogen atom scattering from a semiconductor surface: Ge(111) c (2 × 8). Experiments show bimodal energy-loss distributions revealing two channels. Molecular dynamics trajectories within the Born–Oppenheimer approximation reproduce one channel quantitatively. The second channel transfers much more energy and is absent in simulations. It grows with hydrogen atom incidence energy and exhibits an energy-loss onset equal to the Ge surface bandgap. This leads us to conclude that hydrogen atom collisions at the surface of a semiconductor are capable of promoting electrons from the valence to the conduction band with high efficiency. Our current understanding fails to explain these observations.