arXiv subjects

Paul Brumer

Publications and source records attributed to Paul Brumer.

At least 37 records · Page 2Linked to original sources

arXiv2023

Coherent Control of ultracold molecular collisions: The role of resonances

We consider the coherent control of ultracold molecule-molecule scattering, impacted by a dense set of rovibrational resonances. To characterize the resonance spectrum, a rudimentary model based on multichannel quantum defect theory has been used to study the control of the scattering cross section and the reaction rate. Complete control around resonance energies is shown to be possible, but thermal averaging over a large number of resonances significantly reduces the extent of control of reaction rates due to the random distribution of optimal control parameters between resonances. We show that measuring the extent of coherent control could be used to extract meaningful information about the relative contribution of direct scattering versus collision complex formation, as well as about the statistical regime.

physics.atom-ph↗

arXiv2022

Electronic-vibrational resonance does not alter steady-state transport in natural light-harvesting systems

Oscillations in time-dependent 2D electronic spectra appear as evidence of quantum coherence in light-harvesting systems related to electronic-vibrational resonant interactions. Nature, however, takes place in a non-equilibrium steady-state, so the relevance of these arguments to the natural process is unclear. Here we examine the role of intramolecular vibrations in the non-equilibrium steady-state of photosynthetic dimers in the natural scenario of incoherent light excitation. It is found that vibrations resonant with the energy difference between exciton states do not increase the quantum yield nor the imaginary part of the intersite coherence that is relevant for transport compared with non-resonant vibrations in the natural non-equilibrium steady state. That is, the vibration-electronic resonance interaction does not alter energy transport under natural incoherent-light excitation conditions.

quant-ph↗

arXiv2022

Quantum Kinetic Rates within the Nonequilibrium Steady State

The nonequilibrium steady state (NESS) of a quantum network is central to a host of physical and biological scenarios. Examples include natural processes such as vision and photosynthesis, as well as technical devices such as photocells, both activated by incoherent light (e.g. sunlight) and leading to quantum transport. Here, a completely general approach to defining components of a quantum network in the NESS, and obtaining rates of processes between these components is provided. Quantum effects are explicitly included throughout, both in (a) defining network components via projection operators, and (b) in determining the role of coherences in rate processes. As examples, the methodology is applied to model cases, two versions of the V-level system, and to the spin-boson model, wherein the role of the environment and of internal system properties in determining the rates is examined. In addition, the role of Markovian vs. non-Markovian contributions is quantified, exposing conditions under which NESS rates can be obtained by perturbing the nonequilibrium steady state.

quant-ph↗

arXiv2022

Steady State Photoisomerization Quantum Yield of Model Rhodopsin: Insights from Wavepacket Dynamics?

We simulate the nonequilibrium steady state \textit{cis-trans} photoisomerization of retinal chromophore in rhodopsin based on a two-state-two-mode model coupled to a thermal environment. By analyzing the systematic trends within an inhomogeneously broadened ensemble of systems, we find that the steady state reaction quantum yield (QY) correlates strongly with the excess energy above the crossing point of the system, in agreement with the prediction of the short time dynamical wavepacket picture. However, the nontrivial dependence of the QY on the system-environment interaction indicates that a pure dynamical picture is insufficient and that environment-induced partial internal energy redistribution takes place before the reaction concludes. These results imply that a proper treatment of the photoisomerization reaction, particularly its high QY, must account for the redistribution and dissipation of energy beyond the dynamical wavepacket motion that is typically employed in the literature and that is appropriate only in the transient regime.

physics.chem-ph↗

arXiv2021

Fully differentiable optimization protocols for non-equilibrium steady states

In the case of quantum systems interacting with multiple environments, the time-evolution of the reduced density matrix is described by the Liouvillian. For a variety of physical observables, the long-time limit or steady state solution is needed for the computation of desired physical observables. For inverse design or optimal control of such systems, the common approaches are based on brute-force search strategies. Here, we present a novel methodology, based on automatic differentiation, capable of differentiating the steady state solution with respect to any parameter of the Liouvillian. Our approach has a low memory cost, and is agnostic to the exact algorithm for computing the steady state. We illustrate the advantage of this method by inverse designing the parameters of a quantum heat transfer device that maximizes the heat current and the rectification coefficient. Additionally, we optimize the parameters of various Lindblad operators used in the simulation of energy transfer under natural incoherent light. We also present a sensitivity analysis of the steady state for energy transfer under natural incoherent light as a function of the incoherent-light pumping rate.

quant-ph↗

arXiv2021

Noise-Induced Coherence in Molecular Processes

Excitation of molecules by incident incoherent electromagnetic radiation, such as sunlight, is described in detail and contrasted with the effect of coherent (e.g. laser) light. The nature of the quantum coherences induced by the former, relevant to transport processes in nature and in technology, is emphasized. Both equilibrium and steady state scenarios are discussed, Three examples: simple models, calcium excitation in polarized light, and the isomerization of retinal in rhodopsin are used to expose the underlying qualitative nature of the established coherences.

quant-ph↗

arXiv2021

Extreme Parametric Sensitivity in the Steady-State Photoisomerization of Model Retinal

The photoisomerization reaction of the retinal chromophore in rhodopsin was computationally studied using a two-state two-mode model coupled to thermal baths. Reaction quantum yields at the steady state (10 ps and beyond) were found to be considerably different than their transient values, suggesting a weak correlation between transient and steady-state dynamics in these systems. Significantly, the steady-state quantum yield was highly sensitive to minute changes in system parameters, while transient dynamics was nearly unaffected. Correlation of such sensitivity with standard level spacing statistics of the nonadiabatic vibronic system suggests a possible origin in quantum chaos. The feasibility of experimental observation of this phenomenon and its implications in condensed-phase photochemistry and biological light sensing are discussed.

quant-ph↗

arXiv2021

Multi-objective optimization for retinal photoisomerization models with respect to experimental observables

The fitting of physical models is often done only using a single target observable. However, when multiple targets are considered, the fitting procedure becomes cumbersome, there being no easy way to quantify the robustness of the model for all different observables. Here, we illustrate that one can jointly search for the best model for each desired observable through multi-objective optimization. To do so we construct the Pareto front to study if there exists a set of parameters of the model that can jointly describe multiple, or all, observables. To alleviate the computational cost, the predicted error for each targeted objective is approximated with a Gaussian process model, as it is commonly done in the Bayesian optimization framework. We applied this methodology to improve three different models used in the simulation of stationary state $cis-trans$ photoisomerization of retinal in rhodopsin. Optimization was done with respect to different experimental measurements, including emission spectra, peak absorption frequencies for the $cis$ and $trans$ conformers, and the energy storage.

physics.chem-ph↗

arXiv2021

Near-threshold scaling of resonant inelastic collisions at ultralow temperatures

We show that the cross sections for a broad range of resonant {\it inelastic} processes accompanied by excitation exchange (such as spin-exchange, Förster resonant, or angular momentum exchange) exhibit an unconventional near-threshold scaling $E^{Δm_{12}}$, where $E$ is the collision energy, $Δm_{12}=m_1'+m_2'-m_1-m_2$, and $m_i$ and $m_i'$ are the initial and final angular momentum projections of the colliding species ($i=1,\,2$). In particular, the inelastic cross sections for $Δm_{12}=0$ transitions display an unconventional $E^0$ scaling similar to that of elastic cross sections, and their rates vanish as $T^{Δm_{12}+1/2}$. For collisions dominated by even partial waves (such as those of identical bosons in the same internal state) the scaling is modified to $σ_\text{inel}\propto E^{Δm_{12} +1} $ if $Δm_{12}$ is odd. We present accurate quantum scattering calculations that illustrate these modified threshold laws for resonant spin exchange in ultracold Rb+Rb and O$_2$+O$_2$ collisions. Our results illustrate that the threshold scaling of collision cross sections is determined only by the energetics of the underlying process (resonant vs. exothermic) rather than by whether the internal states of colliding particles is changed in the collision.

physics.atom-ph↗

arXiv2021

Generalized Adiabatic Theorems: Quantum Systems Driven by Modulated Time-Varying Fields

We present generalized adiabatic theorems for closed and open quantum systems that can be applied to slow modulations of rapidly varying fields, such as oscillatory fields that occur in optical experiments and light induced processes. The generalized adiabatic theorems show that a sufficiently slow modulation conserves the dynamical modes of time dependent reference Hamiltonians. In the limiting case of modulations of static fields, the standard adiabatic theorems are recovered. Applying these results to periodic fields shows that they remain in Floquet states rather than in energy eigenstates. More generally, these adiabatic theorems can be applied to transformations of arbitrary time-dependent fields, by accounting for the rapidly varying part of the field through the dynamical normal modes, and treating the slow modulation adiabatically. As examples, we apply the generalized theorem to (a) predict the dynamics of a two level system driven by a frequency modulated resonant oscillation, a pathological situation beyond the applicability of earlier results, and (b) to show that open quantum systems driven by slowly turned-on incoherent light, such as biomolecules under natural illumination conditions, can only display coherences that survive in the steady state.

quant-ph↗

arXiv2021

Computational approaches to efficient generation of the stationary state for incoherent light excitation

Light harvesting processes are often computationally studied from a time-dependent viewpoint, in line with ultrafast coherent spectroscopy experiments. Yet, natural processes take place in the presence of incoherent light, which induces a stationary state. Such stationary states can be described using the eigenbasis of the molecular Hamiltonian, but for realistic systems a full diagonalization is prohibitively expensive. We propose three efficient computational approaches to obtaining the stationary state that circumvent system Hamiltonian diagonalization. The connection between the incoherent perturbations, decoherence, and Kraus operators is established.

physics.chem-ph↗

arXiv2021

Coherent control mechanisms of Penning and associative ionization in cold He$^({2}^3\text{S})$-He$^({2}^3\text{S})$ reactive scattering

We explore coherent control of Penning and associative ionization in cold collisions of metastable He$^*({2}^3\text{S})$ atoms via the quantum interference between different states of the He$_2^*$ collision complex. By tuning the preparation coefficients of the initial atomic spin states, we can benefit from the quantum interference between molecular channels to maximize or minimize the cross sections for Penning and associative ionization. In particular, we find that we can enhance the ionization ratio by 30% in the cold regime. This work is significant for the coherent control of chemical reactions in the cold and ultracold regime.

quant-ph↗

arXiv2020

Complete quantum coherent control of ultracold molecular collisions

We show that quantum interference-based coherent control is a highly efficient tool for tuning ultracold molecular collision dynamics, and is free from the limitations of commonly used methods that rely on external electromagnetic fields. By varying {the relative populations and} phases of an initial coherent superpositions of degenerate molecular states, we demonstrate complete coherent control over integral scattering cross sections in the ultracold $s$-wave regime of both the initial and final collision channels. The proposed control methodology is applied to ultracold O$_2$~+~O$_2$ collisions, showing extensive control over $s$-wave spin-exchange cross sections and product branching ratios over many orders of magnitude.

physics.atom-ph↗

arXiv2020

Inverse design of dissipative quantum steady-states with implicit differentiation

Inverse design of a property that depends on the steady-state of an open quantum system is commonly done by grid-search type of methods. In this paper we present a new methodology that allows us to compute the gradient of the steady-state of an open quantum system with respect to any parameter of the Hamiltonian using the implicit differentiation theorem. As an example, we present a simulation of a spin-boson model where the steady-state solution is obtained using Redfield theory.

quant-ph↗

arXiv2020

Coherent control of reactive scattering at low temperatures: Signatures of quantum interference in the differential cross sections for F + H2 and F + HD

Fundamental entanglement related challenges have prevented quantum interference-based control (i.e. coherent control) of collisional cross sections from being implemented in the laboratory. Here, differential cross sections for reactive scattering at low temperatures are shown to provide a unique opportunity to display such interference-based control by forming coherent superpositions of degenerate rotational states of reactant molecules |jmi with different m. In particular, we identify and quantify a unique signature of coherent control in reactive scattering with applications to F + H2 ! H + HF and HF + D F + HD ! HD + F at 11 K. Control is shown to be extensive.

physics.chem-ph↗

arXiv2020

Energy transfer under natural incoherent light: Effects of asymmetry on efficiency

The non-equilibrium stationary coherences that form in donor-acceptor systems are investigated to determine their relationship to the efficiency of energy transfer to a neighboring reaction center. It is found that the effects of asymmetry in the dimer are generally detrimental to the transfer of energy. Four types of systems are examined, arising from combinations of localized trapping, delocalized (Forster) trapping, eigenstate dephasing and site basis dephasing. In the cases of site basis dephasing the interplay between the energy gap of the excited dimer states and the environment is shown to give rise to a turnover effect in the efficiency under weak dimer coupling conditions. Furthermore, the nature of the coherences and associated flux are interpreted in terms of pathway interference effects. In addition, regardless of the cases considered, the ratio of the real part and the imaginary part of the coherences in the energy-eigenbasis tends to a constant value in the steady state limit.

physics.chem-ph↗

arXiv2020

Steady-state Fano coherences in a V-type system driven by polarized incoherent light

We explore the properties of steady-state Fano coherences generated in a three-level V-system continuously pumped by polarized incoherent light in the absence of coherent driving. The ratio of the stationary coherences to excited-state populations $\mathcal{C} = (1+\frac{Δ^2}{γ(r+γ)} )^{-1}$ is maximized when the excited-state splitting $Δ$ is small compared to either the spontaneous decay rate $γ$ or the incoherent pumping rate $r$. We demonstrate that an intriguing regime exists where the $\mathcal{C}$ ratio displays a maximum as a function of the dephasing rate $γ_d$. We attribute the surprising dephasing-induced enhancement of stationary Fano coherences to the environmental suppression of destructive interference of individual incoherent excitations generated at different times. We identify the imaginary Fano coherence with the non-equilibrium flux across a pair of qubits coupled to two independent thermal baths, unraveling a direct connection between the seemingly unrelated phenomena of incoherent driving of multilevel quantum systems and non-equilibrium quantum transport in qubit networks. The real part of the steady-state Fano coherence is found to be proportional to the deviation of excited-state populations from their values in thermodynamic equilibrium, making it possible to observe signatures of steady-state Fano coherences in excited-state populations. We put forward an experimental proposal for observing steady-state Fano coherences by detecting the total fluorescence signal emitted by Calcium atoms excited by polarized vs. isotropic incoherent light. Our analysis paves the way toward further theoretical and experimental studies of non-equilibrium coherent steady states in thermally driven atomic and molecular systems, and for the exploration of their potential role in biological processes.

quant-ph↗

arXiv2019

Equilibrium Coherence in the Multi-level Spin-boson Model

Interaction between a quantum system and its environment can induce stationary coherences -- off-diagonal elements in the reduced system density matrix -- even at equilibrium. This work investigates the ``quantumness'' of such phenomena by examining the ability of classical and semiclassical models to describe equilibrium stationary coherence in the multi-level spin boson (MLSB) model, a common model for light-harvesting systems. A well justified classical harmonic oscillator model is found to fail to capture equilibrium coherence. This failure is attributed to the effective weakness of classical system-bath interactions due to the absence of a discrete system energy spectrum and, consequently, of quantized shifts in oscillator coordinates. Semiclassical coherences also vanish for a dimeric model with parameters typical of biological light-harvesting, i.e., where both system sites couple to the bath with the same reorganization energy. In contrast, equilibrium coherence persists in a fully quantum description of the same system, suggesting a uniquely quantum-mechanical origin for equilibrium stationary coherence in, e.g., photosynthetic systems. Finally, as a computational tool, a perturbative expansion is introduced that, at third order in $\hbar$, gives qualitatively correct behavior at ambient temperatures for all configurations examined.

quant-ph↗