Asymmetry Control in a Parametric Oscillator for the Quantum Simulation of Chemical Activation
Alejandro Cros Carrillo de Albornoz, Rodrigo G. Cortiñas, Max Schäfer, Nicholas Frattini, Brandon Allen, Delmar G. A. Cabral, Pablo E. Videla, Pouya Khazaei, Eitan Geva, Víctor S. Batista, Michel Devoret
Dissipative tunneling remains a cornerstone effect in quantum mechanics. In chemistry, it plays a crucial role in governing the rates of chemical reactions, often modeled as the motion along the reaction coordinate from one potential well to another. The relative positions of energy levels in these wells strongly influence the reaction dynamics. Chemical research will benefit from a fully adjustable, asymmetric double-well equipped with precise measurement capabilities of the tunneling rates. In this paper, we show a quantum simulator system that consists of a continuously driven Kerr parametric oscillator with a third-order nonlinearity that can be operated in the quantum regime to create a fully tunable asymmetric double-well. Our experiment leverages a low-noise, all-microwave control system with a high-efficiency readout, based on a tunnel Josephson junction circuit, of the which-well information. We explore the reaction rates across the landscape of tunneling resonances in parameter space. We uncover two counter-intuitive effects: (i) a weak asymmetry can significantly decrease the activation rates, even though the well in which the system is initialized is made shallower, and (ii) the width of the tunneling resonances alternates between narrow and broad lines as a function of the well depth and asymmetry. We predict by numerical simulations that both effects will also manifest themselves in ordinary chemical double-well systems in the quantum regime. Our work is a first step for the development of analog molecule simulators of proton transfer reactions based on quantum parametric processes.
Dissipative tunneling remains a cornerstone effect in quantum mechanics. In chemistry, it plays a crucial role in governing the rates of chemical reactions, often modeled as the motion along the reaction coordinate from one potential well to another. The relative positions of energy levels in these wells strongly influence the reaction dynamics. Chemical research will benefit from a fully adjustable, asymmetric double-well equipped with precise measurement capabilities of the tunneling rates. In this paper, we show a quantum simulator system that consists of a continuously driven Kerr parametric oscillator with a third-order nonlinearity that can be operated in the quantum regime to create a fully tunable asymmetric double-well. Our experiment leverages a low-noise, all-microwave control system with a high-efficiency readout, based on a tunnel Josephson junction circuit, of the which-well information. We explore the reaction rates across the landscape of tunneling resonances in parameter space. We uncover two counter-intuitive effects: (i) a weak asymmetry can significantly decrease the activation rates, even though the well in which the system is initialized is made shallower, and (ii) the width of the tunneling resonances alternates between narrow and broad lines as a function of the well depth and asymmetry. We predict by numerical simulations that both effects will also manifest themselves in ordinary chemical double-well systems in the quantum regime. Our work is a first step for the development of analog molecule simulators of proton transfer reactions based on quantum parametric processes.
Chemical reactions are commonly described by the reactive flux transferring the population from reactants to products across a double-well free energy barrier. Dynamics often involves barrier recrossing and quantum effects like tunneling, zero-point energy motion, and interference, which traditional rate theories, such as transition-state theory, do not consider. In this study, we investigate the feasibility of simulating reaction dynamics using a parametrically driven bosonic superconducting Kerr-cat device. This approach provides control over parameters defining the double-well free energy profile, as well as external factors like temperature and the coupling strength between the reaction coordinate and the thermal bath of nonreactive degrees of freedom. We demonstrate the effectiveness of this protocol by showing that the dynamics of proton-transfer reactions in prototypical benchmark model systems, such as hydrogen-bonded dimers of malonaldehyde and DNA base pairs, could be accurately simulated on the currently accessible Kerr-cat devices.
The spontaneous switching of a quantum particle between the wells of a double-well potential is a phenomenon of general interest to physics and chemistry. It was broadly believed that the switching rate decreases steadily as a function of the size of the energy barrier. This view was challenged by a recent experiment on a driven superconducting Kerr nonlinear oscillator (often called the Kerr-cat qubit or the Kerr parametric oscillator), whose energy barrier can be continuously increased by ramping up the drive. Remarkably, as the drive amplitude increases, the switching rate exhibits a steplike decrease termed the ``staircase.'' The view challenged by the experimental staircase demands a deep review of our understanding of the role of quantum effects in double wells. In this work, we use a Lindbladian model of dissipation to derive a semianalytical formula for the switching rate, resolving a continuous transition between tunneling-dominated dynamics and dissipation-dominated dynamics. These two dynamics are observed respectively in the flat part and the steep part of each step in the staircase. Our formula exposes two distinct dissipative processes that limit tunneling: the dephasing of interwell superpositions freezes tunneling via the quantum Zeno effect, and the decay from one excited state to another limits the time during which tunneling can be attempted. This physical understanding allows us to pinpoint the critical drive amplitude that separates the flat and steep part of each step using an equation involving the rates of the two dissipative processes and the tunnel splitting. In addition, analyzing the transition matrix elements in the formula shows that in the regime of a few ($\ensuremath{\lesssim}10$) states in the well and under moderate to low temperatures, highly excited states are populated predominantly via cascaded and direct thermal heating rather than quantum heating. At very low temperatures, we find that the perturbation induced by the non-Hermitian Hamiltonian part of the Lindbladian model becomes increasingly important and facilitates a form of quantum heating that has not been identified before. We numerically map the activation mechanism as a function of drive amplitude, damping rate, and temperature. Our theory deepens the understanding of switching dynamics between metastable quantum states, highlights the importance of a general interplay between tunneling and dissipation, and identifies a novel quantum regime in activated transitions.
Modeling chemical dynamics is essential for understanding, predicting, and optimizing chemical processes. Because realistic chemical systems involve many interacting degrees of freedom, direct propagation of the many-body Schr"{o}dinger equation is intractable for all but the smallest systems. Quantum information platforms offer a fundamentally different representation: a d-dimensional state may be encoded using k=log2(d) qubits rather than storing each amplitude independently. To harness this advantage for chemistry, it is necessary to develop quantum algorithms and hardware architectures capable of simulating the open-system dynamics ubiquitous in condensed-phase and molecular environments. In the first chapter, we develop a theoretical framework for simulating a cavity-modified photoinduced charge-transfer reaction in the carotenoid–porphyrin–C60 (CPC60) molecular triad dissolved in tetrahydrofuran (THF). Nonequilibrium Fermi’s Golden Rule (NE-FGR) rate coefficients are obtained as a product of cavity-free and cavity-modified correlation functions. We further introduce an approximation based on Instantaneous Marcus Theory (IMT) that closely tracks the full NE-FGR result across all relevant time scales. Population transfer rates computed from the population-only off-diagonal quantum master equation (p-tcl-OD-QME) are shown to be consistent with the NE-FGR predictions. Our results demonstrate that nonequilibrium charge-transfer dynamics are significantly modified by coupling to an optical cavity. The second chapter addresses the integration of linear nonautonomous ordinary differential equations on digital quantum hardware. Rather than classically constructing a nonunitary propagator at each time step and embedding it into a larger unitary operation for execution on quantum hardware, we eliminate this classical–quantum partitioning. We derive and propagate differential equations for the singular value decomposition (SVD) factors of the propagator directly, enabling time evolution to be implemented within a quantum-compatible framework. This approach shifts the locus of time integration from the classical processor to the quantum device. In the third chapter, we investigate the feasibility of simulating chemical reaction dynamics on a parametrically driven bosonic superconducting Kerr-cat device. This analog platform enables direct control over parameters defining an effective double-well free-energy landscape, as well as over environmental factors such as temperature and system–bath coupling strength. We demonstrate that proton transfer dynamics in prototypical benchmark systems, including hydrogen-bonded dimers of malonaldehyde and DNA base pairs, can be accurately reproduced using experimentally accessible Kerr-cat architectures.
The ability to efficiently simulate a variety of interacting quantum systems on a single device is an overarching goal for digital and analog quantum simulators. In circuit quantum electrodynamical systems, strongly nonlinear superconducting oscillators are typically realized using transmon qubits, featuring a wide range of tunable couplings that are mainly achieved via flux-dependent inductive elements. Such controllability is highly desirable both for digital quantum information processing and for analog quantum simulations of various physical phenomena, such as arbitrary spin-spin interactions. Furthermore, broad tunability facilitates the study of driven-dissipative oscillator dynamics in previously unexplored parameter regimes. In this work, we demonstrate the ability to selectively activate different dynamical regimes between two strongly nonlinear oscillators using parametric modulation. In particular, our scheme enables access to regimes that are dominated by photon-hopping, two-mode squeezing, or cross-Kerr interactions. Finally, we observe level repulsion and attraction between Kerr-nonlinear oscillators in regimes where the nonlinearities exceed the coupling strengths and decay rates of the system. Our results could be used for realizing purely analog quantum simulators to study arbitrary spin systems as well as for exploring strongly nonlinear oscillator dynamics in previously unexplored interaction regimes.
By applying a microwave drive to a specially designed Josephson circuit, we have realized a double-well model system: a Kerr oscillator submitted to a squeezing force. We have observed, for the first time, the spectroscopic fingerprint of a quantum double-well Hamiltonian when its barrier height is increased: a pairwise level kissing (coalescence) corresponding to the exponential reduction of tunnel splitting in the excited states as they sink under the barrier. The discrete levels in the wells also manifest themselves in the activation time across the barrier which, instead of increasing smoothly as a function of the barrier height, presents steps each time a pair of excited states is captured by the wells. This experiment illustrates the quantum regime of Arrhenius’s law, whose observation is made possible here by the unprecedented combination of low dissipation, time-resolved state control, 98.5% quantum nondemolition single shot measurement fidelity, and complete microwave control over all Hamiltonian parameters in the quantum regime. Direct applications to quantum computation and simulation are discussed. Published by the American Physical Society 2024
The ultimate regularity of quantum mechanics creates a tension with the assumption of classical chaos used in many of our pictures of chemical reaction dynamics. Out-of-time-order correlators (OTOCs) provide a quantum analog to the Lyapunov exponents that characterize classical chaotic motion. Maldacena, Shenker, and Stanford have suggested a fundamental quantum bound for the rate of information scrambling, which resembles a limit suggested by Herzfeld for chemical reaction rates. Here, we use OTOCs to study model reactions based on a double-well reaction coordinate coupled to anharmonic oscillators or to a continuum oscillator bath. Upon cooling, as one enters the tunneling regime where the reaction rate does not strongly depend on temperature, the quantum Lyapunov exponent can approach the scrambling bound and the effective reaction rate obtained from a population correlation function can approach the Herzfeld limit on reaction rates: Tunneling increases scrambling by expanding the state space available to the system. The coupling of a dissipative continuum bath to the reaction coordinate reduces the scrambling rate obtained from the early-time OTOC, thus making the scrambling bound harder to reach, in the same way that friction is known to lower the temperature at which thermally activated barrier crossing goes over to the low-temperature activationless tunneling regime. Thus, chemical reactions entering the tunneling regime can be information scramblers as powerful as the black holes to which the quantum Lyapunov exponent bound has usually been applied.