arXiv subjects

Patricia Vindel-Zandbergen

Publications and source records attributed to Patricia Vindel-Zandbergen.

12 recordsLinked to original sources

arXiv2026

Photonic architectures for synthetic chiral light-driven chiral sensing

Molecular chirality gives rise to left- and right-handed enantiomers whose balance underpins biochemical function. Deviations from this enantiomeric excess are promising biomarkers of disease. Despite its importance, rapid and sensitive detection of enantiomeric excess in trace amounts of small chiral molecules remains an outstanding challenge. Synthetic chiral light introduces new opportunities for chiroptical spectroscopy, with the potential to enhance light-matter interactions by several orders of magnitude. Here we propose a new class of photonic architectures for synthetic chiral light, in which photonic structures generate, guide and optimize chiral light-matter interactions. As a first realization, we show that hollow dielectric waveguides support phase-matched propagation of multicolor fields enabling coherent accumulation of the enantio-sensitive nonlinear response over centimeter-scale distances. By combining microscopic quantum-response simulations with Maxwell's equations, we predict that incident pulse energies of around 1 uJ produce hundreds of picojoules of third-harmonic emission from only picomole quantities of carvone gas at 50 mbar over just 2 cm of propagation, with enantio-sensitive contrast approaching 5%. Phase-resolved Fourier analysis isolates a background-free chiral signal exhibiting the maximum possible dichroism of 200%. Beyond efficient chiral sensing, photonic architectures for synthetic chiral light establish a scalable platform for integrated nonlinear chiral spectroscopy, molecular fingerprinting based on ultrafast electron dynamics, and topologically robust chiroptical observables.

physics.optics↗

arXiv2026

Topologically protected chiral sensing using Synthetic Chiral Light

Chirality underlies molecular function in living matter, yet its optical detection remains challenging because conventional chiroptical spectroscopies rely on weak corrections to the dominant electric-dipole light-matter interaction, making desired optical signals weak and fragile. Topology offers a route to robustness, enabling observables whose defining properties survive disorder and imperfections. However, experimental realization of a practical topological observable for chiral spectroscopy has remained elusive. Here we realize chiral topological light and demonstrate such an observable. A tightly focused, phase-locked, counter-rotating two-colour field encodes chirality in the three-dimensional electric-field trajectory while its dominant topological charge resides in the longitudinal electric-field component where it remains hidden from direct far-field detection. An isotropic chiral medium acts as a topological transducer, converting the latent topology of the driving field into a propagating nonlinear response whose topological charge becomes directly observable in the far field while remaining strongly suppressed in achiral media. Using randomly oriented chiral single-crystal powders, we experimentally detect the enantio-sensitive response through the topological charge of the emitted field. Directly accessible in the far field and robust against experimental imperfections, this observable allows us to track and control chiral signal on attosecond timescales through the relative phase of the driving two-colour fields. Our results establish topology as a practical resource for ultrafast chiral optical spectroscopy.

physics.chem-ph↗

arXiv2026

Direct Asymmetric Photochemistry with Synthetic Chiral Light

Circularly polarized light has long been used to distinguish the two mirror images of chiral molecules. Recently, a conceptual breakthrough has predicted that a new form of optical fields - synthetic chiral light - could usher in an 'electric-dipole revolution' in chiroptical interactions. We report the first experimental evidence for this prediction in the optical domain, using a three-dimensional laser electric field synthesized to trace a chiral pattern. The ionization and fragmentation of chiral molecules was found to depend on both the molecular handedness, and the handedness and geometry of the synthetic chiral field. Supported by two theoretical models, our results demonstrate that synthetic chiral light can induce strong chiroptical interactions, opening new horizons for asymmetric photochemistry and chiral analysis.

physics.chem-ph↗

arXiv2026

Perspective on a challenge: predicting the photochemistry of cyclobutanone

This Perspective is part of a Special Topic that explored the maturity of nonadiabatic molecular dynamics for predicting photochemical processes. In 2023, a prediction challenge was issued to the community of computational photochemists to simulate the photochemistry of cyclobutanone, photoexcited at 200 nm, and the resulting time-resolved MeV-UED signal. The challenge attracted 15 theoretical predictions from more than 70 researchers, employing a wide range of strategies for electronic structure and nonadiabatic molecular dynamics to predict the time-resolved MeV-UED signal before the experiment had been conducted at SLAC (Stanford, USA). The MeV-UED instrument at Shanghai Jiao Tong University was also used to provide a second independent time-resolved MeV-UED signal for the photochemistry of cyclobutanone. This Perspective discusses the various approaches and strategies used by the participants to predict the photochemistry of cyclobutanone. This work also summarizes the strengths and weaknesses of various methods used for photoexcitation, electronic structure, nonadiabatic dynamics, and calculation of observables, as agreed by the participants during a CECAM workshop dedicated to the results of the challenge and organized in Lausanne in April 2025. This Perspective also collects all the predicted time-resolved MeV-UED signals into a single figure, together with the experimental signal. This challenge (i) demonstrated the qualitative predictive power of nonadiabatic molecular dynamics and (ii) underscore the impact of electronic-structure theory on the outcome of the excited-state dynamics and the need for its careful benchmarking. This effort allowed the community to share practical strategies to perform nonadiabatic dynamics (discussed in the present Perspective) and constitutes a 'calibration' exercise for computational photochemistry.

physics.chem-ph↗

arXiv2025

Roadmap for Molecular Benchmarks in Nonadiabatic Dynamics

Simulating the coupled electronic and nuclear response of a molecule to light excitation requires the application of nonadiabatic molecular dynamics. However, when faced with a specific photophysical or photochemical problem, selecting the most suitable theoretical approach from the wide array of available techniques is not a trivial task. The challenge is further complicated by the lack of systematic method comparisons and rigorous testing on realistic molecular systems. This absence of comprehensive molecular benchmarks remains a major obstacle to advances within the field of nonadiabatic molecular dynamics. A CECAM workshop, Standardizing Nonadiabatic Dynamics: Towards Common Benchmarks, was held in May 2024 to address this issue. This Perspective highlights the key challenges identified during the workshop in defining molecular benchmarks for nonadiabatic dynamics. Specifically, this work outlines some preliminary observations on essential components needed for simulations and proposes a roadmap aiming to establish, as an ultimate goal, a community-driven, standardized molecular benchmark set.

physics.chem-ph↗

arXiv2025

All-optical coherent control of chiral electronic transitions for highly enantioselective photochemistry

Enantioselective photochemistry provides access to unique molecular structures and functions, with deep implications for fundamental science and industrial applications. Current methods for highly enantioselective photochemistry critically rely on chiral sensitisers, as circularly polarised light on its own yields vanishingly weak enantioselectivity. Here, we introduce a quantum control strategy to drive highly enantioselective electronic excitations in randomly oriented samples using a pulsed ($\sim$22 fs) IR laser and two of its harmonics, in the absence of intermediate resonances. Our approach addresses electronic transitions, does not require chiral sensitisers, or cold molecules, or long electronic coherence times, is relevant for liquid-phase samples, and remains effective over interaction regions extending across many laser wavelengths, even in the presence of dispersion. We show how, by 3D shaping the field's polarisation over the interaction region, we can achieve enantioselective coherent control over electronic population transfer. Our ab-initio simulations in the chiral molecule carvone yield a selectivity of $\sim$30 % in the populations of the first excited electronic state, three orders-of-magnitude higher than what is possible with circularly polarised light ($\sim$0.01 %). These results bring all-optical enantioselective photochemistry into the realm of practical applications.

physics.chem-ph↗

arXiv2024

Ultrafast TACOS -- Terahertz-Assisted Chiro-Optical Spectroscopy

We bring together the advantages of terahertz (THz) and optical spectroscopies to introduce TACOS (Terahertz-Assisted Chiro-Optical Spectroscopy), a novel approach for ultrafast and highly efficient imaging of molecular chirality and control over chiral electronic dynamics. We show how, using a THz pulse, we can induce a transient electronic orientation in a medium of randomly oriented chiral molecules that breaks the isotropy of the molecular sample. This symmetry breaking twists the nonlinear response of the medium to an ultrashort linearly polarised optical pulse in a highly enantiosensitive manner. As a result, the medium emits elliptically polarised light at new optical frequencies that records the molecular handedness via purely electric-dipole interactions. The long wavelength and period of the THz pulse enable both spatial coherence across the sample and a substantial degree of electronic orientation over the duration of the ultrashort optical pulse. TACOS does not require optical carrier-envelope phase stability or working in vacuum, and it creates exciting avenues for ultrafast and highly efficient chiral sensing and manipulation.

physics.optics↗

arXiv2024

Non adiabatic dynamics of photoexcited cyclobutanone: predicting structural measurements from trajectory surface hopping with XMS-CASPT2 simulations

For years, theoretical calculations and scalable computer simulations have complemented ultrafast experiments as they offer the advantage to overcome experimental restrictions and have access to the whole dynamics. This synergy between theory and experiment promises to yield a deeper understanding of photochemical processes, offering valuable insights into the behavior of complex systems at the molecular level. However, the capacity of theoretical models to predict ultrafast experimental outcomes has remained largely unexplored. In this work, we aim to predict the electron diffraction signals of an upcoming ultrafast photochemical experiment using high-level electronic structure calculations and non adiabatic dynamics simulations. In particular, we perform trajectory surface hopping with XMSCASPT2 simulations for understanding mechanistic photodissociation of cyclobutanone upon excitation at 200 nm.

physics.chem-ph↗

arXiv2023

Different Flavors of Exact-Factorization-Based Mixed Quantum-Classical Methods for Multistate Dynamics

The exact factorization approach has led to the development of new mixed quantum-classical methods for simulating coupled electron-ion dynamics. We compare their performance for dynamics when more than two electronic states are occupied at a given time, and analyze: (1) the use of coupled versus auxiliary trajectories in evaluating the electron-nuclear correlation terms, (2) the approximation of using these terms within surface-hopping and Ehrenfest frameworks, and (3) the relevance of the exact conditions of zero population transfer away from nonadiabatic coupling regions and total energy conservation. Dynamics through the three-state conical intersection in the uracil radical cation as well as polaritonic models in one dimension are studied.

quant-ph↗

arXiv2022

Exact-Factorization-Based Surface-Hopping for Multi-State Dynamics

A surface-hopping algorithm recently derived from the exact factorization approach, SHXF, [Ha, Lee, Min, J. Phys. Chem. Lett. 9, 1097 (2018)] introduces an additional term in the electronic equation of surface-hopping, which couples electronic states through the quantum momentum. This term not only provides a first-principles description of decoherence but here we show it is crucial to accurately capture non-adiabatic dynamics when more than two states are occupied at any given time. Using a vibronic coupling model of the uracil cation, we show that the lack of this term in traditional surface-hopping methods, including those with decoherence-corrections, leads to failure to predict the dynamics through a three-state intersection, while SHXF performs similarly to the multi-configuration time-dependent Hartree quantum dynamics benchmark.

physics.chem-ph↗

arXiv2021

A study of the decoherence correction derived from the exact factorization approach for non-adiabatic dynamics

We present a detailed study of the decoherence correction to surface-hopping that was recently derived from the exact factorization approach. Ab initio multiple spawning calculations that use the same initial conditions and same electronic structure method are used as a reference for three molecules: ethylene, methaniminium cation, and fulvene, for which non-adiabatic dynamics follows a photo-excitation. A comparison with the Granucci-Persico energy-based decoherence correction, and the augmented fewest-switches surface-hopping scheme shows that the three decoherence-corrected methods operate on individual trajectories in a qualitatively different way, but results averaged over trajectories are similar for these systems.

physics.chem-ph↗

arXiv2017

Tunneling induced electron transfer between separated protons

We study electron transfer between two separated nuclei using local control theory. By conditioning the algorithm in a symmetric system formed by two protons, one can favored slow transfer processes, where tunneling is the main mechanism, achieving transfer efficiencies close to unity assuming fixed nuclei. The solution can be parametrized using sequences of pump and dump pi pulses, where the pump pulse is used to excite the electron to a highly excited state where the time for tunneling to the target nuclei is on the order of femtoseconds. The time delay must be chosen to allow for full population transfer via tunneling, and the dump pulse is chosen to remove energy from the state to avoid tunneling back to the original proton. Finally, we study the effect of the nuclear kinetic energy on the transfer efficiency. Even in the absence of relative motion between the protons, the spreading of the nuclear wave function is enough to reduce the yield of electronic transfer to less than one half.

quant-ph↗