arXiv subjects

Simon Huppert

Publications and source records attributed to Simon Huppert.

16 recordsLinked to original sources

arXiv2026

Vibrational Activation Triggers Ultrafast Excited State Intramolecular Proton Transfer in Single-Benzene Fluorophores

Single-benzene fluorophores (SBFs) are exceptionally light-weight quantum emitters which have recently been shown to display Excited State Intramolecular Proton Transfer (ESIPT) and highly tunable dual-fluorescence that could be exploited for multiple applications. Here, we employ excited-state molecular dynamics to investigate the ultrafast dynamics of ESIPT in two different SBFs, one of which with a new structure proposed in this work. We find that both single and double ultrafast proton transfers can be triggered by exciting specific molecular vibrations. Strikingly, the kinetic activation of these vibrations - selected by atomistic, symmetry-based analysis - can considerably enhance the yield of proton transfer(s), as well as direct the reaction towards either single or double-transfer products. In-depth analysis elucidates the origins of this vibronic control, providing atomistic guidelines through which both the rate and fate of ESIPT could be steered using ultrafast IR-Vis spectroscopies.

physics.chem-ph↗

arXiv2025

Probing the partition function for temperature-dependent potentials with nested sampling

Thermodynamic properties can be in principle derived from the partition function, which, in many-atom systems, is hard to evaluate as it involves a sum on the accessible microscopic states. Recently, the partition function has been computed via nested sampling, relying on Bayesian statistics, which is able to provide the density of states as a function of the energy in a single run, independently of the temperature. This appealing property is lost whenever the potential energy that appears in the partition function is temperature-dependent: for instance, mean-field effective potential energies or the quantum partition function in the path-integral formalism. For these cases, the nested sampling must be carried out at each temperature, which results in a massive increase of computational time. Here, we introduce and implement a new method, that is based on an extended partition function where the temperature is considered as an additional parameter to be sampled. The extended partition function can be evaluated by nested sampling in a single run, so to restore this highly desirable property even for temperature-dependent effective potential energies. We apply this original method to compute the quantum partition function for harmonic potentials and Lennard-Jones clusters at low temperatures and show that it outperforms the straightforward application of nested sampling for each temperature within several temperature ranges.

physics.comp-ph↗

arXiv2025

Impact and Interplay of Quantum Coherence and Dissipative Dynamics for Isotope Effects in Excited-State Intramolecular Proton Transfer

The quantum dynamics of Excited State Intramolecular Proton Transfer (ESIPT) is studied using a non-Markovian open quantum system perspective. Models of 2-(2-hydroxyphenyl) benzothiazole (HBT) and 10-hydroxybenzo[h]quinoline (HBQ) are adapted from Zhang et al. (ACS Phys. Chem. Au, 3, 107-118 (2023)) and simulated via the numerically exact TEDOPA Matrix Product State formalism, using a newly developed framework for continuous degrees of freedom subject to dissipation. The quantum treatment of the proton wave packet shows a counter-intuitive kinetic isotope effect, with strong isotope dependence for the barrierless potential surface of HBQ and no isotope effect in the double-well energy landscape of the HBT, in accordance with experimental results. Strikingly, for HBQ we find that changing laser pulse durations can even reverse the isotope effect on the proton transfer rate, revealing the role of vibration-assisted absorption in ESIPT. This study highlights the often neglected effect of excitation conditions on ESIPT, as well as the role of entangled, vibrationally assisted absorption processes that can be directly visualised in our multidimensional treatment of the full electro-vibronic-environment wave function.

physics.chem-ph↗

arXiv2025

The Q-AMOEBA (CF) Polarizable Potential

We present Q-AMOEBA (CF), an enhanced version of the Q-AMOEBA polarizable model that integrates a geometry-dependent charge flux (CF) term while designed for an explicit treatment of nuclear quantum effects (NQE). The inclusion of CF effects allows matching experimental data for the molecular structure of water in both gas and liquid phases, addressing limitations faced by most force fields. We show that Q-AMOEBA (CF) provides highly accurate results for a wide range of thermodynamical properties of liquid water. Using the computational efficiency of the adaptive Quantum Thermal Bath method, which accounts for NQE at a cost comparable to classical molecular dynamics, we evaluate the robustness and transferability of Q-AMOEBA (CF) by calculating hydration free energies of various ions and organic molecules. Finally, we apply this methodology to the alanine dipeptide and compute the corresponding dihedral angle potential of mean force and hydration free energy. Unexpectedly, the latter quantity displays significant NQE. These results pave the way to a finer understanding of their role in biochemical systems.

physics.chem-ph↗

arXiv2024

Optical and X-ray Photo-emission Spectroscopies of Core/Shell Colloidal CdSe/CdS Quantum Dots: Modeling and Experimental Determination of Band Alignment

Optical properties of multilayer semi-conductor nano-emitters are crucially dependent on the relative energy levelsof their different components. For core/shell quantum dots, the relative energy difference between conduction bandedge of core and shell materials induces, depending on its value, either a confinement of the electron within the coreor a delocalization of its wave function within the whole quantum dot. This results in drastic consequences on theenergy and the oscillator strength of the fundamental transition. Surprisingly, the literature currently lacks a definitivevalue for the energy difference between CdSe and CdS conduction band edges as most of the experimental studiesprovide values corresponding to specific geometries of quantum dots. Here, we develop a full theoretical modelexpressing energy levels considering core/shell interface pressure, ligands and enabling the accurate prediction ofthe bandgap value with the nanocrystal size. It allows to reliably determine the energy difference between theconduction band edge of CdSe and CdS materials, known as the conduction band offset, in such a way that this valuecan later be used to model quantum dots of any geometry. This value is determined using our model and two differentexperimental methods: optical spectroscopy and X-ray photoemission (XPS) experiments.

cond-mat.mtrl-sci↗

arXiv2024

Extending Non-Perturbative Simulation Techniques for Open-Quantum Systems to Excited-State Proton Transfer and Ultrafast Non-Adiabatic Dynamics

Excited state proton transfer is an ubiquitous phenomenon in biology and chemistry, spanning from the ultrafast reactions of photo-bases and acids to light-driven, enzymatic catalysis and photosynthesis. However, the simulation of such dynamics involves multiple challenges, since high-dimensional, out-of-equilibrium vibronic states play a crucial role, while a fully quantum description of the proton's dissipative, real-space dynamics is also required. In this work, we extend the powerful Matrix Product State approach to open quantum systems (TEDOPA) to study these demanding dynamics, and also more general non-adiabatic processes that can appear in complex photochemistry subject to strong laser driving. As an illustration, we initially consider an open model of a four-level electronic system interacting with hundreds of intramolecular vibrations that drive ultrafast excited state proton transfer, as well as an explicit photonic environment that allows us to directly monitor the resulting dual fluorescence in this system. We then demonstrate how to include a continuous 'reaction coordinate' of the proton transfer that allows numerically exact simulations that can be understood, visualized and interpreted in the familiar language of diabatic and adiabatic dynamics on potential surfaces, while also retaining an exact quantum treatment of dissipation and driving effects that could be used to study diverse problems in ultrafast photochemistry.

physics.chem-ph↗

arXiv2023

When Quantum Fluctuations Meet Structural Instabilities: The Isotope- and Pressure-Induced Phase Transition in the Quantum Paraelectric NaOH

Anhydrous sodium hydroxide, a common and structurally simple compound, shows spectacular isotope effects: NaOD undergoes a first-order transition, which is absent in NaOH. By combining ab initio electronic structure calculations with path integrals, we show that NaOH is an unusual example of a quantum paraelectric: zero-point quantum fluctuations stretch the weak hydrogen bonds (HBs) until they become unstable and break. By strengthening HBs via isotope substitution or applied pressure, the system can be driven down to a broken-symmetry antiferroelectric phase. We also provide a simple quantitative criterion for HB breaking in layered crystals and show that nuclear quantum effects are crucial in paraelectric to ferroelectric transitions in hydrogen-bonded hydroxides.

cond-mat.mtrl-sci↗

arXiv2022

Routine Molecular Dynamics Simulations Including Nuclear Quantum Effects: from Force Fields to Machine Learning Potentials

We report the implementation of a multi-CPU and multi-GPU massively parallel platform dedicated to the explicit inclusion of nuclear quantum effects (NQEs) in the Tinker-HP molecular dynamics (MD) package. The platform, denoted Quantum-HP, exploits two simulation strategies: the Ring-Polymer Molecular Dynamics (RPMD) that provides exact structural properties at the cost of a MD simulation in an extended space of multiple replicas, and the adaptive Quantum Thermal Bath (adQTB) that imposes the quantum distribution of energy on a classical system via a generalized Langevin thermostat and provides computationally affordable and accurate (though approximate) NQEs. We discuss some implementation details, efficient numerical schemes, parallelization strategies and quickly review the GPU acceleration of our code. Our implementation allows an efficient inclusion of NQEs in MD simulations for very large systems, as demonstrated by scaling tests on water boxes with more than 200,000 atoms (simulated using the AMOEBA polarizable force field). We test the compatibility of the approach with Tinker-HP's recently introduced Deep-HP machine learning potentials module by computing water properties using the DeePMD potential with adQTB thermostating. Finally, we show that the platform is also compatible with the alchemical free energy estimation capabilities of Tinker-HP and fast enough to perform simulations. Therefore, we study how the NQEs affect the hydration free energy of small molecules solvated with the recently developed Q-AMOEBA water force field. Overall, the Quantum-HP platform allows users to perform routine quantum MD simulations of large condensed-phase systems and will participate to shed a new light on the quantum nature of important interactions in biological matter.

physics.chem-ph↗

arXiv2022

Improving Condensed Phase Water Dynamics with Explicit Nuclear Quantum Effects: the Polarizable Q-AMOEBA Force Field

We introduce a new parametrization of the AMOEBA polarizable force field for water denoted Q-AMOEBA, for use in simulations that explicitly account for nuclear quantum effects (NQEs). This study is made possible thanks to the recently introduced adaptive Quantum Thermal Bath (adQTB) simulation technique which computational cost is comparable to classical molecular dynamics. The flexible Q-AMOEBA model conserves the initial AMOEBA functional form, with an intermolecular potential including an atomic multipole description of electrostatic interactions (up to quadrupole), a polarization contribution based on the Thole interaction model and a buffered 14-7 potential to model van der Waals interactions. It has been obtained by using a Force Balance fitting strategy including high-level quantum chemistry reference energies and selected condensed phase properties targets. The final Q-AMOEBA model is shown to accurately reproduce both gas phase and condensed phase properties, notably improving the original AMOEBA water model. This development allows the fine study of NQEs on water liquid phase properties such as the average H-O-H angle compared to its gas phase equilibrium value, isotope effects etc... Q-AMOEBA also provides improved infrared spectroscopy prediction capabilities compared to AMOEBA03. Overall, we show that the impact of NQEs depends on the underlying model functional form and on the associated strength of hydrogen bonds. Since adQTB simulations can be performed at near classical computational cost using the Tinker-HP package, Q-AMOEBA can be extended to organic molecules, proteins and nucleic acids opening the possibility for the large scale study of the importance of NQEs in biophysics.

physics.chem-ph↗

arXiv2021

Nuclear Quantum Effects in liquid water at near classical computational cost using the adaptive Quantum Thermal Bath

We demonstrate the accuracy and efficiency of a recently introduced approach to account for nuclear quantum effects (NQE) in molecular simulations: the adaptive Quantum Thermal Bath (adQTB). In this method, zero point energy is introduced through a generalized Langevin thermostat designed to precisely enforce the quantum fluctuation-dissipation theorem. We propose a refined adQTB algorithm with improved accuracy and we report adQTB simulations of liquid water. Through extensive comparison with reference path integral calculations, we demonstrate that it provides excellent accuracy for a broad range of structural and thermodynamic observables as well as infrared vibrational spectra. The adQTB has a computational cost comparable to classical molecular dynamics, enabling simulations of up to millions of degrees of freedom.

physics.chem-ph↗

arXiv2020

Semiconductor quantum plasmonics

We investigate the frontier between classical and quantum plasmonics in highly doped semiconductor layers. The choice of a semiconductor platform instead of metals for our study permits an accurate description of the quantum nature of the electrons constituting the plasmonic response, which is a crucial requirement for quantum plasmonics. Our quantum model allows us to calculate the collective plasmonic resonances from the electronic states determined by an arbitrary one-dimensional potential. Our approach is corroborated with experimental spectra, realized on a single quantum well, in which higher order longitudinal plasmonic modes are present. We demonstrate that their energy depends on the plasma energy, as it is also the case for metals, but also on the size confinement of the constituent electrons. This work opens the way towards the applicability of quantum engineering techniques for semiconductor plasmonics.

cond-mat.mes-hall↗

arXiv2020

Quantum driven proton diffusion in brucite-like minerals under high pressure

We investigate the elementary steps at the microscopic level for proton diffusion in brucite under high pressure, which results from a complex interplay between two processes: the O-H reorientations motion around the $\mathbf c$ axis and O-H covalent bond dissociations. First-principle path-integral molecular dynamics simulations reveal that the increasing pressure tends to lock the former motion, while, in contrast, it activates the latter which is mainly triggered by nuclear quantum effects. These two competing effects therefore give rise to a pressure sweet spot for proton diffusion within the mineral. In brucite \ce{Mg(OH)2}, proton diffusion reaches a maximum for pressures close to 70GPa, while the structurally similar portlandite \ce{Ca(OH)2} never shows proton diffusion within the pressure range and time scale that we explored. We analyze the different behaviors of brucite and portlandite, which might constitute two prototypes for other minerals with the same structure.

cond-mat.mtrl-sci↗

arXiv2016

Single photon superradiance and cooperative Lamb shift in an optoelectronic device

Single photon superradiance is a strong enhancement of spontaneous emission appearing when a single excitation is shared between a large number of two-level systems. This enhanced rate can be accompanied by a shift of the emission frequency, the cooperative Lamb shift, issued from the exchange of virtual photons between the emitters. In this work we present a semiconductor optoelectronic device allowing the observation of these two phenomena at room temperature. We demonstrate experimentally and theoretically that plasma oscillations in spatially separated quantum wells interact through real and virtual photon exchange. This gives rise to a superradiant mode displaying a large cooperative Lamb shift.

cond-mat.mes-hall↗

arXiv2016

Strong and ultra-strong coupling with free space radiation

Strong and ultra-strong light-matter coupling are remarkable phenomena of quantum electrodynamics occurring when the interaction between a matter excitation and the electromagnetic field cannot be described by usual perturbation theory. This is generally achieved by coupling an excitation with large oscillator strength to the confined electromagnetic mode of an optical microcavity. In this work we demonstrate that strong/ultra-strong coupling can also take place in the absence of optical confinement. We have studied the non-perturbative spontaneous emission of collective excitations in a dense two-dimensional electron gas that superradiantly decays into free space. By using a quantum model based on the input-output formalism, we have derived the linear optical properties of the coupled system and demonstrated that its eigenstates are mixed light-matter particles, like in any system displaying strong or ultra-strong light-matter interaction. Moreover, we have shown that in the ultra-strong coupling regime, i.e. when the radiative broadening is comparable to the matter excitation energy, the commonly used rotating-wave and Markov approximations yield unphysical results. Finally, the input-output formalism has allowed us to prove that Kirchhoff's law, describing thermal emission properties, applies to our system in all the light-matter coupling regimes considered in this work.

quant-ph↗

arXiv2015

Radiatively broadened thermal emitters

We study the incandescence of a semiconductor system characterized by a radiatively broadened material excitation. We show that the shape of the emission spectrum and the peak emissivity value are determined by the ratio between radiative and non-radiative relaxation rates of the material mode. Our system is a heavily doped quantum well, exhibiting a collective bright electronic excitation in the mid-infrared. The spontaneous emission rate of this collective mode strongly depends on the emission direction and, uncommonly for a solid-state system, can dominate non-radiative scattering processes. Consequently the incandescence spectrum undergoes strong modifications when the detection angle is varied. Incandescence is modelled solving quantum Langevin equations, including a microscopic description of the collective excitations, decaying into electronic and photonic baths. We demonstrate that the emissivity reaches unity value for a well-defined direction and presents an angular radiative pattern which is very different from that of an oscillating dipole.

cond-mat.mes-hall↗

arXiv2015

Terahertz emission from multiple-microcavity exciton-polariton lasers

Terahertz emission between exciton-polariton branches in semiconductor microcavities is expected to be strongly stimulated in the polariton laser regime, due to the high density of particles in the lower state (final state stimulation effect). However, non-radiative scattering processes depopulate the upper state and greatly hinder the efficiency of such terahertz sources. In this work, we suggest a new scheme using multiple microcavities and exploiting the transition between two interband polariton branches located below the exciton level. We compare the non-radiative processes loss rates in single and double cavity devices and we show that a dramatic reduction can be achieved in the latter, enhancing the efficiency of the terahertz emission.

cond-mat.mes-hall↗