Daniel M. Reich’s research while affiliated with Freie Universität Berlin and other places

In photoelectron circular dichroism (PECD) it is generally difficult to trace how and when the chirality of the molecule is imprinted onto the photoelectron. We present simulations of PECD in a simple model and employ chirality measures to establish a quantitative connection between the chirality of the potential, the electronic wave function's chirality, and the anisotropy of the photoelectron distribution. We show that these measures are suitable indicators for chirality, paving the way for tracking the chiral evolution from the nuclear scaffold to the final observable. Published by the American Physical Society 2025

Quantum chemical calculations of one‐photon absorption, electronic circular dichroism and anisotropy factor spectra for the A‐band transition of fenchone, camphor and 3‐methylcyclopentanone (3MCP) are reported. While the only weakly allowed nature of the transition leads to comparatively large anisotropies, a proper theoretical description of the absorption for such a transition requires to account for non‐Condon effects. We present experimental data for the anisotropy of 3MCP in the liquid phase and show that corresponding Herzberg–Teller corrections are critical to reproduce the main experimental features. The results obtained with our comprehensive theoretical model highlight the importance of the vibrational degree of freedom, paving the way for a deeper understanding of the dynamics in electronic circular dichroism.

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. After reviewing several classes of spherical quadrature methods in terms of their efficiency and error distribution, we derive guidelines for choosing the best quadrature method for orientation averages and illustrate these with three examples from chiral molecule physics. While Gauss quadratures allow for achieving numerically exact integration for a wide range of applications, other methods offer advantages in specific circumstances. Our guidelines can also be applied to higher-dimensional spherical domains and other geometries. We also present a Python package providing a flexible interface to a variety of quadrature methods.

Quantum resonances in collisions and reactions are a sensitive probe of the intermolecular forces. They may dominate the final quantum state distribution, as recently observed for Feshbach resonances in a cold collision experiment (Science 380, 77 (2023)). This raises the question whether the sensitivity of such measurements is sufficient to assess the quality of theoretical models for the interaction. We here compare measured collision cross sections to those obtained with exact quantum coupled-channels scattering calculations for three different ab initio potential energy surfaces. We find that the ability to test the correct prediction of energy redistribution over molecular degrees of freedom is within reach, requiring only a modest improvement in energy resolution of current experiments. Such improvement will enable the separation of individual resonances and allow for an unambiguous experimental test of different theory approaches.

In molecular physics, it is often necessary to average over the orientation of molecules when calculating observables, in particular when modelling 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. After reviewing several classes of spherical quadrature methods in terms of their efficiency and error distribution, we derive guidelines for choosing the best quadrature method for orientation averages and illustrate these with three examples from chiral molecule physics. While Gauss quadratures allow for achieving numerically exact integration for a wide range of applications, other methods offer advantages in specific circumstances. Our guidelines can also by applied to higher-dimensional spherical domains and other geometries. We also present a Python package providing a flexible interface to a variety of quadrature methods.

Photoelectron circular dichroism (PECD) originates from the interplay between a molecule's chiral nuclear scaffold and a circularly polarized ionizing laser field. It is one of the most sensitive characterization techniques for the chirality of molecules in the gas phase. However, due to the complexity of the observable, it is generally difficult to predict and track how and when the chirality of the molecule is imprinted onto the photoelectron. Here, we present simulations of PECD for single-photon ionization in a hydrogenic single-electron model with an artificial chiral potential. This framework allows us to systematically tune the system's chirality and characterize the emergence of PECD. To this end, we propose chirality measures for potentials and wave functions to establish a quantitative connection with the resulting anisotropy in the photelectron distribution. We show that these chirality measures are suitable indicators for chirality in our model, paving the way for tracking the evolution of chirality from the nuclear scaffold to the final observable.

Quantum chemical calculations of one-photon absorption, electronic circular dichroism and anisotropy factor spectra for the A-band transition of fenchone, camphor and 3-methylcyclopentanone (3MCP) are reported. While the only weakly allowed nature of the transition leads to comparatively large anisotropies, a proper theoretical description of the absorption for such a transition requires to account for non-Condon effects. We present experimental data for the anisotropy of 3MCP in the liquid phase and show that corresponding Herzberg-Teller corrections are critical to reproduce the main experimental features. The results obtained with our comprehensive theoretical model highlight the importance of the vibrational degree of freedom, paving the way for a deeper understanding of the dynamics in electronic circular dichroism.

Operator controllability refers to the ability to implement an arbitrary unitary in SU(N) and is a prerequisite for universal quantum computing. Controllability tests can be used in the design of quantum devices to reduce the number of external controls. Their practical use is hampered, however, by the exponential scaling of their numerical effort with the number of qubits. Here, we devise a hybrid quantum-classical algorithm based on a parametrized quantum circuit. We show that controllability is linked to the number of independent parameters, which can be obtained by dimensional expressivity analysis. We exemplify the application of the algorithm to qubit arrays with nearest-neighbour couplings and local controls. Our work provides a systematic approach to the resource-efficient design of quantum chips.

We derive a set of functionals for optimization towards an arbitrary cat state and demonstrate their application by optimizing the dynamics of a Kerr-nonlinear Hamiltonian with two-photon driving. The versatility of our framework allows us to adapt our functional towards optimization of maximally entangled cat states, applying it to a Jaynes-Cummings model. We identify the strategy of the obtained control fields and determine the quantum speed limit as a function of the cat state's excitation. Finally, we extend our optimization functionals to open quantum system dynamics and apply it to the Jaynes-Cummings model with decay on the oscillator. For strong dissipation and large cat radii, we find a change in the control strategy compared to the case without dissipation. Our results highlight the power of optimal control with functionals specifically crafted for complex physical tasks and the versatility of the quantum optimal control toolbox for practical applications in the quantum technologies.

Correction for 'Increasing ion yield circular dichroism in femtosecond photoionisation using optimal control theory' by Manel Mondelo-Martell et al., Phys. Chem. Chem. Phys., 2022, 24, 9286-9297, https://doi.org/10.1039/D1CP05239J.