Numerical evaluation of orientation averages and its application to molecular physics.

In molecular physics, it is often necessary to average over the orientation of molecules when calculating observables, in particular when modeling experiments in the liquid or gas phase. Evaluated in terms of Euler angles, this is closely related to integration over two- or three-dimensional unit spheres, a common problem discussed in numerical analysis. The computational cost of the integration depends significantly on the quadrature method, making the selection of an appropriate method crucial for the feasibility of simulations.

Improving potential energy surfaces using measured Feshbach resonance states.

The structure and dynamics of a molecular system is governed by its potential energy surface (PES), representing the total energy as a function of the nuclear coordinates. Obtaining accurate potential energy surfaces is limited by the exponential scaling of Hilbert space, restricting quantitative predictions of experimental observables from first principles to small molecules with just a few electrons. Here, we present an explicitly physics-informed approach for improving and assessing the quality of families of PESs by modifying them through linear coordinate transformations based on experimental data.

Correction: Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory.

Correction for 'Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory' by Manel Mondelo-Martell , , 2022, , 9286-9297, https://doi.org/10.1039/D1CP05239J.

Tomography of Feshbach resonance states.

Feshbach resonances are fundamental to interparticle interactions and become particularly important in cold collisions with atoms, ions, and molecules. In this work, we present the detection of Feshbach resonances in a benchmark system for strongly interacting and highly anisotropic collisions: molecular hydrogen ions colliding with noble gas atoms. The collisions are launched by cold Penning ionization, which exclusively populates Feshbach resonances that span both short- and long-range parts of the interaction potential.

Pump-probe spectroscopy of chiral vibrational dynamics.

A planar molecule may become chiral upon excitation of an out-of-plane vibration, changing its handedness during half a vibrational period. When exciting such a vibration in an ensemble of randomly oriented molecules with an infrared laser, half of the molecules will undergo the vibration phase-shifted by π compared to the other half, and no net chiral signal is observed. This symmetry can be broken by exciting the vibrational motion with a Raman transition in the presence of a static electric field.

Rydberg Atom-Enabled Spectroscopy of Polar Molecules via Förster Resonance Energy Transfer.

Non-radiative energy transfer between a Rydberg atom and a polar molecule can be controlled by a static electric field. Here, we show how to exploit this control for state-resolved, non-destructive detection and spectroscopy of the molecules, where the lineshape reflects the type of molecular transition. Using the example of ammonia, we identify the conditions for collision-mediated spectroscopy in terms of the required electric field strengths, relative velocities, and molecular densities.

Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory.

We investigate how optimal control theory can be used to improve Circular Dichroism (CD) signals for the A-band of fenchone measured the photoionization yield upon further excitation. These transitions are electric dipole forbidden to first order, which translates into low population transfer to the excited state but allows for a clearer interplay between electric and magnetic transition dipole moments, which are of the same order of magnitude. Using a model including the electronic ground and excited A state as well as all permanent and transition multipole moments up to the electric quadrupole, we find that the absolute CD signal of randomly oriented molecules can be increased by a factor of 2.

Resource-Efficient Dissipative Entanglement of Two Trapped-Ion Qubits.

We demonstrate a simplified method for dissipative generation of an entangled state of two trapped-ion qubits. Our implementation produces its target state faster and with higher fidelity than previous demonstrations of dissipative entanglement generation and eliminates the need for auxiliary ions. The entangled singlet state is generated in ∼7  ms with a fidelity of 0.

Determining the nature of quantum resonances by probing elastic and reactive scattering in cold collisions.

Scattering resonances play a central role in collision processes in physics and chemistry. They help build an intuitive understanding of the collision dynamics due to the spatial localization of the scattering wavefunctions. For resonances that are localized in the reaction region, located at short separation behind the centrifugal barrier, sharp peaks in the reaction rates are the characteristic signature, observed recently with state-of-the-art experiments in low-energy collisions.

Phase protection of Fano-Feshbach resonances.

Decay of bound states due to coupling with free particle states is a general phenomenon occurring at energy scales from MeV in nuclear physics to peV in ultracold atomic gases. Such a coupling gives rise to Fano-Feshbach resonances (FFR) that have become key to understanding and controlling interactions-in ultracold atomic gases, but also between quasiparticles, such as microcavity polaritons. Their energy positions were shown to follow quantum chaotic statistics.

Optimized sampling of mixed-state observables.

Quantum dynamical simulations of statistical ensembles pose a significant computational challenge due to the fact that mixed states need to be represented. If the underlying dynamics is fully unitary, for example, in ultrafast coherent control at finite temperatures, then one approach to approximate time-dependent observables is to sample the density operator by solving the Schrödinger equation for a set of wave functions with randomized phases. We show that, on average, random-phase wave functions perform well for ensembles with high mixedness, whereas at higher purities a deterministic sampling of the energetically lowest-lying eigenstates becomes superior.

Perfect control of photoelectron anisotropy for randomly oriented ensembles of molecules by XUV REMPI and polarization shaping.

We report two schemes to generate perfect anisotropy in the photoelectron angular distribution of a randomly oriented ensemble of polyatomic molecules. In order to exert full control over the anisotropy of photoelectron emission, we exploit interferences between single-photon pathways and a manifold of resonantly enhanced two-photon pathways. These are shown to outperform nonsequential (ω, 2ω) bichromatic phase control for the example of CHFClBr molecules.

Principles of enantio-selective excitation in three-wave mixing spectroscopy of chiral molecules.

Three-wave mixing spectroscopy of chiral molecules, which exist in left-handed and right-handed conformations, allows for enantioselective population transfer despite random orientation of the molecules. This is based on constructive interference of the three-photon pathways for one enantiomer and the destructive one for the other. We prove here that three mutually orthogonal polarization directions are required to this end.

Quantum Control of Photoelectron Circular Dichroism.

We demonstrate coherent control over the photoelectron circular dichroism in randomly oriented chiral molecules, based on quantum interference between multiple photoionization pathways. To significantly enhance the chiral signature, we use a finite manifold of indistinguishable (1+1^{'}) resonantly enhanced multiphoton ionization pathways interfering at a common photoelectron energy but probing different intermediate states. We show that this coherent control mechanism maximizes the number of molecular states that constructively contribute to the dichroism at an optimal photoelectron energy and thus outperforms other schemes, including interference between opposite-parity pathways driven by bichromatic (ω, 2ω) fields as well as sequential pump-probe ionization.

Controlling open quantum systems: tools, achievements, and limitations.

The advent of quantum devices, which exploit the two essential elements of quantum physics, coherence and entanglement, has sparked renewed interest in the control of open quantum systems. Successful implementations face the challenge of preserving relevant nonclassical features at the level of device operation. A major obstacle is decoherence, which is caused by interaction with the environment.

Photoassociation Spectroscopy in Penning Ionization Reactions at Sub-Kelvin Temperatures.

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 reaction's 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 interparticle separation.

Molecular hydrogen interacts more strongly when rotationally excited at low temperatures leading to faster reactions.

The role of internal molecular degrees of freedom, such as rotation, has scarcely been explored experimentally in low-energy collisions despite their significance to cold and ultracold chemistry. Particularly important to astrochemistry is the case of the most abundant molecule in interstellar space, hydrogen, for which two spin isomers have been detected, one of which exists in its rotational ground state whereas the other is rotationally excited. Here we demonstrate that quantization of molecular rotation plays a key role in cold reaction dynamics, where rotationally excited ortho-hydrogen reacts faster due to a stronger long-range attraction.

Exploiting Non-Markovianity for Quantum Control.

Quantum technology, exploiting entanglement and the wave nature of matter, relies on the ability to accurately control quantum systems. Quantum control is often compromised by the interaction of the system with its environment since this causes loss of amplitude and phase. However, when the dynamics of the open quantum system is non-Markovian, amplitude and phase flow not only from the system into the environment but also back.

Coherent Control of Bond Making.

We demonstrate coherent control of bond making, a milestone on the way to coherent control of photoinduced bimolecular chemical reactions. In strong-field multiphoton femtosecond photoassociation experiments, we find the yield of detected magnesium dimer molecules to be enhanced for positively chirped pulses and suppressed for negatively chirped pulses. Our ab initio model shows that control is achieved by purification combined with chirp-dependent Raman transitions.

Controlling magnetic Feshbach resonances in polar open-shell molecules with nonresonant light.

Magnetically tunable Feshbach resonances for polar paramagnetic ground-state diatomics are too narrow to allow for magnetoassociation starting from trapped, ultracold atoms. We show that nonresonant light can be used to engineer the Feshbach resonances in their position and width. For nonresonant field intensities of the order of 10(9) W/cm(2), we find the width to be increased by 3 orders of magnitude, reaching a few Gauss.

Optimal strategies for estimating the average fidelity of quantum gates.

We show that the minimum experimental effort to estimate the average error of a quantum gate scales as 2(n) for n qubits and requires classical computational resources ∼n(2)2(3n) when no specific assumptions on the gate can be made. This represents a reduction by 2(n) compared to the best currently available protocol, Monte Carlo characterization. The reduction comes at the price of either having to prepare entangled input states or obtaining bounds rather than the average fidelity itself.

Femtosecond two-photon photoassociation of hot magnesium atoms: a quantum dynamical study using thermal random phase wavefunctions.

Two-photon photoassociation of hot magnesium atoms by femtosecond laser pulses, creating electronically excited magnesium dimer molecules, is studied from first principles, combining ab initio quantum chemistry and molecular quantum dynamics. This theoretical framework allows for rationalizing the generation of molecular rovibrational coherence from thermally hot atoms [L. Rybak, S.

Rovibrational dynamics of the strontium molecule in the A(1)Σ(u)+, c(3)Π(u), and a(3)Σ(u)+ manifold from state-of-the-art ab initio calculations.

State-of-the-art ab initio techniques have been applied to compute the potential energy curves for the electronic states in the A(1)Σ(u)(+), c(3)Π(u), and a(3)Σ(u)(+) manifold of the strontium dimer, the spin-orbit and nonadiabatic coupling matrix elements between the states in the manifold, and the electric transition dipole moment from the ground X(1)Σ(g)(+) to the nonrelativistic and relativistic states in the A+c+a manifold. The potential energy curves and transition moments were obtained with the linear response (equation of motion) coupled cluster method limited to single, double, and linear triple excitations for the potentials and limited to single and double excitations for the transition moments. The spin-orbit and nonadiabatic coupling matrix elements were computed with the multireference configuration interaction method limited to single and double excitations.