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Register a new userObservation of Quantum Effects in sub Kelvin Cold Reactions
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There has been a long-standing quest to observe chemical reactions at low temperatures where reaction rates and pathways are governed by quantum mechanical effects. So far this field of Quantum Chemistry has been dominated by theory. The difficulty has been to realize in the laboratory low enough collisional velocities between neutral reactants, so that the quantum wave nature could be observed. We report here the first realization of merged neutral supersonic beams, and the observation of clear quantum effects in the resulting reactions. We observe orbiting resonances in the Penning ionization reaction of argon and molecular hydrogen with metastable helium leading to a sharp increase in the absolute reaction rate in the energy range corresponding to a few degrees kelvin down to 10 mK. Our method is widely applicable to many canonical chemical reactions, and will enable a breakthrough in the experimental study of Quantum Chemistry.
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Penning ionization reactions in merged beams with precisely controlled collision energies have been shown to accurately probe quantum mechanical effects in reactive collisions. A complete microscopic understanding of the reaction is, however, faced with two major challenges---the highly excited character of the reactions entrance channel and the limited precision of even the best state-of-the-art ab initio potential energy surfaces. Here, we suggest photoassociation spectroscopy as a tool to identify the character of orbiting resonances in the entrance channel and probe the ionization width as a function of inter-particle separation. We introduce the basic concept and discuss the general conditions under which this type of spectroscopy will be successful.
Quantum indistinguishability plays a crucial role in many low-energy physical phenomena, from quantum fluids to molecular spectroscopy. It is, however, typically ignored in most high temperature processes, particularly for ionic coordinates, implicitly assumed to be distinguishable, incoherent and thus well-approximated classically. We explore chemical reactions involving small symmetric molecules, and argue that in many situations a full quantum treatment of collective nuclear degrees of freedom is essential. Supported by several physical arguments, we conjecture a Quantum Dynamical Selection (QDS) rule for small symmetric molecules that precludes chemical processes that involve direct transitions from orbitally non-symmetric molecular states. As we propose and discuss, the implications of the Quantum Dynamical Selection rule include: (i) a differential chemical reactivity of para- and ortho-hydrogen, (ii) a mechanism for inducing inter-molecular quantum entanglement of nuclear spins, (iii) a new isotope fractionation mechanism, (iv) a novel explanation of the enhanced chemical activity of Reactive Oxygen Species, (v) illuminating the importance of ortho-water molecules in modulating the quantum dynamics of liquid water, (vi) providing the critical quantum-to-biochemical linkage in the nuclear spin model of the (putative) quantum brain, among others.
Many-body systems relaxing to equilibrium can exhibit complex dynamics even if their steady state is trivial. At low temperatures or high densities their evolution is often dominated by steric hindrances affecting particle motion [1,2,3]. Local rearrangements are highly constrained, giving rise to collective - and often slow - relaxation.This dynamics can be difficult to analyse from first principles, but the essential physical ingredients are captured by idealized lattice models with so- called kinetic constraints [4]. Here we experimentally realize a many-body system exhibiting manifest kinetic constraints and measure its dynamical properties. In the cold Rydberg gas used in our experiments, the nature of the constraints can be tailored through the detuning of the excitation lasers from resonance [5,6,7,8], which controls whether the system undergoes correlated or anti- correlated dynamics. Our results confirm recent theoretical predictions [5,6], and highlight the analogy between the dynamics of interacting Rydberg gases and that of soft-matter systems.
We develop a fully quantum mechanical methodology to describe the static properties and the dynamics of a single anharmonic vibrational mode interacting with a quantized infrared cavity field in the strong and ultrastrong coupling regimes. By comparing multiconfiguration time-dependent Hartree (MCTDH) simulations for a Morse oscillator in a cavity, with an equivalent formulation of the problem in Hilbert space, we describe for the first time the essential role of permanent dipole moments in the femtosecond dynamics of vibrational polariton wavepackets. We show that depending on the shape of the electric dipole function $d_e(q)$ along the vibrational mode coordinate $q$, molecules can be classified into three general families. For molecules that are polar and have a positive slope of the dipole function at equilibrium, we show that an initial diabatic light-matter product state without vibrational or cavity excitations can evolve into a polariton wavepacket with a large number of intracavity photons, for interaction strengths at the onset of ultrastrong coupling. This build up of intracavity photon amplitude is accompanied by an effective $lengthening$ of the vibrational mode of nearly $10%$, comparable with a laser-induced vibrational excitation in free space. In contrast, molecules that are also polar at equilibrium but have a negative slope of the dipole function, experience an effective mode $shortening$ under equivalent coupling conditions. Our model predictions are numerically validated using realistic $ab$-$initio$ potentials and dipole functions for HF and CO$_2$ molecules in their ground electronic states. We finally propose a non-adiabatic state preparation scheme to generate vibrational polaritons using nanoscale infrared antennas and UV-vis photochemistry or electron tunneling, to enable the far-field detection of spontaneously generated infrared quantum light.
Anisotropy is a fundamental property of particle interactions. It occupies a central role in cold and ultra-cold molecular processes, where long range forces have been found to significantly depend on orientation in ultra-cold polar molecule collisions. Recent experiments have demonstrated the emergence of quantum phenomena such as scattering resonances in the cold collisions regime due to quantization of the intermolecular degrees of freedom. Although these states have been shown to be sensitive to interaction details, the effect of anisotropy on quantum resonances has eluded experimental observation so far. Here, we directly measure the anisotropy in atom-molecule interactions via quantum resonances by changing the quantum state of the internal molecular rotor. We observe that a quantum scattering resonance at a collision energy of $k_B$ x 270 mK appears in the Penning ionization of molecular hydrogen with metastable helium only if the molecule is rotationally excited. We use state of the art ab initio and multichannel quantum molecular dynamics calculations to show that the anisotropy contributes to the effective interaction only for $H_2$ molecules in the first excited rotational state, whereas rotationally ground state $H_2$ interacts purely isotropically with metastable helium. Control over the quantum state of the internal molecular rotation allows us to switch the anisotropy on or off and thus disentangle the isotropic and anisotropic parts of the interaction. These quantum phenomena provide a challenging benchmark for even the most advanced theoretical descriptions, highlighting the advantage of using cold collisions to advance the microscopic understanding of particle interactions.
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