arXiv subjects

Alex W. Chin

Publications and source records attributed to Alex W. Chin.

At least 19 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↗

arXiv2026

Tensor network methods for non-perturbative dynamics of open quantum systems

The description of open quantum system dynamics beyond the perturbative treatment (usually associated with Markovian master equations) is a computationally challenging task due to the unfavorable exponential scaling of memory kernels. Developed over recent decades in the context of quantum information and condensed matter, tensor networks provide both a new formalism and a toolbox for overcoming previous computational bottlenecks. This framework enables the formulation of non-perturbative, numerically exact methods for describing the dynamics of open quantum systems to controllable numerical accuracy. In this review, we present these methods and discuss their commonalities and differences to paint a comprehensive view of the field.

quant-ph↗

arXiv2026

Revisiting crossed-correlated baths in open quantum systems simulated by HEOM or T-TEDOPA

Excited-state dynamics of open quantum systems is analyzed by the hierarchical equations of motion (HEOM) or the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA) method when a discrete $ab$ $initio$ linear vibronic model is parametrized by continuous temperature-dependent spectral densities leading to crossed correlation functions, i.e. correlated fluctuations of the energy gap collective modes. We focus on a conical intersection involving two collective modes tuning the energy of each excited state and we revisit the transformation of the initial correlated tuning baths to de-correlated shared baths in order to reduce the computational resources. While a completely frequency-dependent transformation poses problems for HEOM, we find that in some particular cases, an optimal approximate frequency-independent transformation may be derived. On the contrary, T-TEDOPA is very efficient and allows to use this frequency-dependent transformation at the price of managing long-range couplings in the tensor chain. An illustrative application is shown by using the linear vibronic coupling model of a planar symmetrical (phenylethynyl)benzene dimer.

quant-ph↗

arXiv2026

First-principles study of dispersive readout in circuit QED

The speed and fidelity of dispersive readout of superconducting qubits should improve by increasing the amplitude of the measurement drive. Experiments show, however, that beyond some drive amplitude there is always a saturation or drop in fidelity, often associated with a decrease in qubit energy relaxation time $T_1$. A simple Lindblad master equation does not capture the latter effect. More involved approaches based on effective master equations rely on strong assumptions about the spectra of the system and the bath and only partially agree with observations. Here, we perform a first-principles simulation of the full unitary dynamics of dispersive readout by considering the circuit QED Hamiltonian coupled to a microscopic model for the measurement transmission line, allowing for its arbitrary spectrum, including filters. Our access to the dynamics of the bath degrees of freedom allows us to investigate the emission spectrum of the system as a function of drive power. We show how the dependence of qubit $T_1$ on readout drive amplitude is sensitive to the details of the bath spectrum. In particular, we find that $T_1$ drops with increasing drive amplitude when a Purcell notch filter is placed at the qubit frequency, and that the Lindblad master equation shows general qualitative defects compared to the first-principles model.

quant-ph↗

arXiv2026

Efficient construction of time-invariant process tensors for simulating high-dimensional non-Markovian open quantum systems

Numerical methods for obtaining exact dynamics of non-Markovian open quantum systems are mostly limited to either small systems or to short-time evolution only. Here, we propose a new algorithm for computing process tensors--matrix product operator (MPO) representations that capture the environment influence--which achieves greatly enhanced computational scalings with system size, while maintaining linear scaling with simulation length. We build on recent developments in the field which allow for long-time evolutions through process tensors which have a time-translational invariance. These can be built for general Gaussian environments and generic coupling operators with the system using infinite time-evolving block decimation (iTEBD). We introduce a modified iTEBD algorithm using intermediate compression steps which bring down the computation time scaling with system size $d$ from $\mathcal{O}(d^8)$ to $\mathcal{O}(d^4)$, as well as significantly lowering the required memory. To illustrate the power of this method, we apply it to the problem of dispersive qubit readout in circuit QED, which was previously out-of-reach numerically. The full treatment of the measurement resonator, which requires a large system space, combined with the long simulation times precipitated by the separation of timescales between the measurement drive and the environment dissipation, is now possible. The algorithm we introduce not only allows for capturing non-Markovian dynamics in large open quantum systems, but also further extends all the existing capabilities of process tensors, for example in quantum optimal control, or in computation of multi-time correlations or of steady states, to more complex systems with tens of levels.

quant-ph↗

arXiv2025

Connectivity matters: Impact of bath modes ordering and geometry in open quantum system simulation with Tensor Network States

Being able to study the dynamics of quantum systems interacting with several environments is important in many settings ranging from quantum chemistry to quantum thermodynamics, through out-of-equilibrium systems. For such problems tensor network-based methods are state-of-the-art approaches for performing numerically exact simulations. However, to be used efficiently in this multi-environment and non-perturbative context, these methods require an optimized choice of the topology of the wave-function Ansätze. This is often done by analysing cross-correlations between different system and environment degrees of freedom. Here, we show for canonical model Hamiltonians that simple orderings of bosonic environmental modes, which enable the joint {System + Environments} state to be written as a matrix product state, considerably reduce the bond dimension required for convergence despite introducing long-ranged interactions. These results suggest that complex correlation analyses for tweaking tensor networks topology (e.g. entanglement renormalization) are usually not necessary and that tree tensor network states are sub-optimal compared to simple matrix product states in many important models of physical open systems.

quant-ph↗

arXiv2025

Extracting Coupling-Mode Spectral Densities with Two-Dimensional Electronic Spectroscopy

Methods for reconstructing the spectral density of a vibrational environment from experimental data can yield key insights into the impact of the environment on molecular function. Although such experimental methods exist, they generally only access vibrational modes that couple diagonally to the electron system. Here we present a method for extracting the spectral density of modes that couple to the transition between electronic states, using two-dimensional electronic spectroscopy. To demonstrate this, we use a process-tensor method that can simulate two-dimensional electronic spectroscopy measurements in a numerically exact way. To explain how the extraction works, we also derive an approximate analytical solution, which illustrates that the non-Markovianity of the environment plays an essential role in the existence of the simulated signal.

physics.chem-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↗

arXiv2024

Process tensor approaches to modeling two-dimensional spectroscopy

Problems in the field of open quantum systems often involve an environment that strongly influences the dynamics of excited states. Here we present a numerical method to model optical spectra of non-Markovian open quantum systems. The method employs a process tensor framework to efficiently compute multi-time correlations in a numerically exact way. To demonstrate the efficacy of our method, we compare 2D electronic spectroscopy simulations produced through our method to Markovian master equation simulations in three different system-bath coupling regimes.

quant-ph↗

arXiv2024

MPSDynamics.jl: Tensor network simulations for finite-temperature (non-Markovian) open quantum system dynamics

The MPSDynamics.jl package provides an easy to use interface for performing open quantum systems simulations at zero and finite temperatures. The package has been developed with the aim of studying non-Markovian open system dynamics using the state-of-the-art numerically exact Thermalized-Time Evolving Density operator with Orthonormal Polynomials Algorithm (T-TEDOPA) based on environment chain mapping. The simulations rely on a tensor network representation of the quantum states as matrix product states (MPS) and tree tensor network (TTN) states. Written in the Julia programming language, MPSDynamics.jl is a versatile open-source package providing a choice of several variants of the Time-Dependent Variational Principle (TDVP) method for time evolution (including novel bond-adaptive one-site algorithms). The package also provides strong support for the measurement of single and multi-site observables, as well as the storing and logging of data, which makes it a useful tool for the study of many-body physics. It currently handles long-range interactions, time-dependent Hamiltonians, multiple environments, bosonic and fermionic environments, and joint system-environment observables.

quant-ph↗

arXiv2024

Managing Temperature in Open Quantum Systems Strongly Coupled with Structured Environments

In non-perturbative non-Markovian open quantum systems, reaching either low temperatures with the hierarchical equations of motion (HEOM) or high temperatures with the Thermalized Time Evolving Density Operator with Orthogonal Polynomials (T-TEDOPA) formalism in Hilbert space remains challenging. We compare different manners of modeling the environment. Sampling the Fourier transform of the bath correlation function, also called temperature dependent spectral density, proves to be very effective. T-TEDOPA (Tamascelli et al. Phys. Rev. Lett. 123, 090402 (2019)) uses a linear chain of oscillators with positive and negative frequencies while HEOM is based on the complex poles of an optimized rational decomposition of the temperature dependent spectral density (Xu et al. Phys. Rev. Lett. 129, 230601 (2022)). Resorting to the poles of the temperature independent spectral density and of the Bose function separately is an alternative when the problem due to the huge number of the Bose poles at low temperature is circumvented. Two examples illustrate the effectiveness of the HEOM and T-TEDOPA approaches: a benchmark pure dephasing case and a two-bath model simulating dynamics of excited electronic states coupled through a conical intersection. We show the efficiency of T-TEDOPA to simulate dynamics at a finite temperature by using either continuous spectral densities or only all the intramolecular oscillators of a linear vibronic model calibrated from ab initio data of a phenylene ethynylene dimer.

quant-ph↗

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↗

arXiv2024

From Non-Markovian Dissipation to Spatiotemporal Control of Quantum Nanodevices

Nanodevices exploiting quantum effects are critically important elements of future quantum technologies (QT), but their real-world performance is strongly limited by decoherence arising from local `environmental' interactions. Compounding this, as devices become more complex, i.e. contain multiple functional units, the `local' environments begin to overlap, creating the possibility of environmentally mediated decoherence phenomena on new time-and-length scales. Such complex and inherently non-Markovian dynamics could present a challenge for scaling up QT, but -- on the other hand -- the ability of environments to transfer `signals' and energy might also enable sophisticated spatiotemporal coordination of inter-component processes, as is suggested to happen in biological nanomachines, like enzymes and photosynthetic proteins. Exploiting numerically exact many body methods (tensor networks) we study a fully quantum model that allows us to explore how propagating environmental dynamics can instigate and direct the evolution of spatially remote, non-interacting quantum systems. We demonstrate how energy dissipated into the environment can be remotely harvested to create transient excited/reactive states, and also identify how reorganisation triggered by system excitation can qualitatively and reversibly alter the `downstream' kinetics of a `functional' quantum system. With access to complete system-environment wave functions, we elucidate the microscopic processes underlying these phenomena, providing new insight into how they could be exploited for energy efficient quantum devices.

physics.bio-ph↗

arXiv2024

Environmentally driven symmetry-breaking quenches dual fluorescence in proflavine

Nonadiabatic couplings between several electronic excited states are ubiquitous in many organic chromophores and can significantly influence optical properties. A recent experimental study demonstrated that the proflavine molecule exhibits surprising dual fluorescence in the gas phase, that is suppressed in polar solvent environments. Here, we uncover the origin of this phenomenon by parameterizing a linear-vibronic coupling (LVC) Hamiltonian from spectral densities of system-bath coupling constructed along molecular dynamics trajectories, fully accounting for interactions with the condensed-phase environment. The finite-temperature absorption, steady-stat emission, and time-resolved emission spectra are then computed using powerful, numerically exact tensor network approaches. We find that the dual fluorescence in vacuum is driven by a single well-defined coupling mode, but is quenched in solution due to dynamic solvent-driven symmetry-breaking that mixes the two low-lying electronic states. We expect the computational framework developed here to be widely applicable to the study of non-Condon effects in complex condensed-phase environments.

physics.chem-ph↗

arXiv2022

Competing oxygen evolution reaction mechanisms revealed by high-speed compressive Raman imaging

Transition metal oxides are state-of-the-art materials for catalysing the oxygen evolution reaction (OER), whose slow kinetics currently limit the efficiency of water electrolysis. However, microscale physicochemical heterogeneity between particles, dynamic reactions both in the bulk and at the surface, and an interplay between particle reactivity and electrolyte makes probing the OER challenging. Here, we overcome these limitations by applying state-of-the-art compressive Raman imaging to uncover competing bias-dependent mechanisms for the OER in a solid electrocatalyst, α-Li2IrO3. By spatially and temporally tracking changes in the in- and out-of-plane Ir-O stretching modes - identified by density functional theory calculations - we follow catalytic activation and charge accumulation following ion exchange under a variety of electrolytes, particle compositions and cycling conditions. We extract velocities of phase fronts and demonstrate that at low overpotentials oxygen is evolved by the combination of an electrochemical-chemical mechanism and a classical electrocatalytic adsorbate mechanism, whereas at high overpotentials only the latter occurs. These results provide strategies to promote mechanisms for enhanced OER performances, and highlight the power of compressive Raman imaging for low-cost, chemically specific tracking of microscale reaction dynamics in a broad range of systems where ion and electron exchange can be coupled to structural changes, i.e. catalysts, battery materials, memristors, etc.

cond-mat.mtrl-sci↗

arXiv2022

Highly tunable optics across a topological transition in organic polymers

Controllable topological phase transitions are appealing as they allow for tunable single particle electronic properties. Here, by using state-of-the-art manybody perturbation theory techniques, we show that the topological $Z_2$ phase transition occurring in the single particle spectrum of the recently synthetized ethynylene bridged polyacene polymers is accompanied by a topological excitonic phase transition: the band inversion in the non-trivial phase yields real-space exciton wave functions in which electrons and holes exchange orbital characters with respect to the trivial phase. The topological excitonic phase transition results in a broad tunability of the singlet-triplet splittings, opening appealing perspectives for the occurrence of singlet fission. Finally, the flatness of the single-particle electronic structure in the topological non trivial phase leads to negatively dispersing triplet excitons in a large portion of the Brillouin zone, opening a route for spontaneously coherent energy transport at room temperature.

cond-mat.mes-hall↗

arXiv2021

Influence of non-adiabatic effects on linear absorption spectra in the condensed phase: Methylene blue

Modeling linear absorption spectra of solvated chromophores is highly challenging as contributions are present both from coupling of the electronic states to nuclear vibrations and solute-solvent interactions. In systems where excited states intersect in the Condon region, significant non-adiabatic contributions to absorption lineshapes can also be observed. Here, we introduce a robust approach to model linear absorption spectra accounting for both environmental and non-adiabatic effects from first principles. This model parameterizes a linear vibronic coupling (LVC) Hamiltonian directly from energy gap fluctuations calculated along molecular dynamics (MD) trajectories of the chromophore in solution, accounting for both anharmonicity in the potential and direct solute-solvent interactions. The resulting system dynamics described by the LVC Hamiltonian are solved exactly using the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA). The approach is applied to the linear absorption spectrum of methylene blue (MB) in water. We show that the strong shoulder in the experimental spectrum is caused by vibrationally driven population transfer between the bright S1 and the dark S2 state. The treatment of the solvent environment is one of many factors which strongly influences the population transfer and lineshape; accurate modeling can only be achieved through the use of explicit quantum mechanical solvation. The efficiency of T-TEDOPA, combined with LVC Hamiltonian parameterizations from MD, leads to an attractive method for describing a large variety of systems in complex environments from first principles.

physics.chem-ph↗

arXiv2021

Optical projection and spatial separation of spin entangled triplet-pairs from the S1 (21Ag-) state of pi-conjugated systems

The S1 (21Ag-) state is an optically dark state of natural and synthetic pi-conjugated materials that can play a critical role in optoelectronic processes such as, energy harvesting, photoprotection and singlet fission. Despite this widespread importance, direct experimental characterisations of the electronic structure of the S1 (21Ag-) wavefunction have remained scarce and uncertain, although advanced theory predicts it to have a rich multi-excitonic character. Here, studying an archetypal polymer, polydiacetylene, and carotenoids, we experimentally demonstrate that S1 (21Ag-) is a superposition state with strong contributions from spin-entangled pairs of triplet excitons (1(TT)). We further show that optical manipulation of the S1 (21Ag-) wavefunction using triplet absorption transitions allows selective projection of the 1(TT) component into a manifold of spatially separated triplet-pairs with lifetimes enhanced by up to one order of magnitude and whose yield is strongly dependent on the level of inter-chromophore coupling. Our results provide a unified picture of 21Ag-states in pi-conjugated materials and open new routes to exploit their dynamics in singlet fission, photobiology and for the generation of entangled (spin-1) particles for molecular quantum technologies.

physics.chem-ph↗