arXiv:2204.08571 · The Journal of Physical Chemistry Letters
Quantum Computation of Hydrogen Bond Dynamics and Vibrational Spectra
Philip Richerme, Melissa Revelle, Christopher G. Yale, Daniel Lobser, Ashlyn D. Burch, Susan Clark, Debadrita Saha, Miguel Angel Lopez-Ruiz, Anurag Dwivedi, Jeremy M. Smith, Sam A. Norrell, Amr Sabry, Srinivasan S. Iyengar
Calculating observable properties of chemical systems is often classically intractable and widely viewed as a promising application of quantum information processing. Here, we introduce a new framework for solving generic quantum chemical dynamics problems using quantum logic. We experimentally demonstrate a proof-of-principle instance of our method using the QSCOUT ion-trap quantum computer, where we experimentally drive the ion-trap system to emulate the quantum wavepacket dynamics corresponding to the shared-proton within an anharmonic hydrogen bonded system. Following the experimental creation and propagation of the shared-proton wavepacket on the ion-trap, we extract measurement observables such as its time-dependent spatial projection and its characteristic vibrational frequencies to spectroscopic accuracy (3.3 cm –1 wavenumbers, corresponding to >99.9% fidelity). Our approach introduces a new paradigm for studying the chemical dynamics and vibrational spectra of molecules and opens the possibility to describe the behavior of complex molecular processes with unprecedented accuracy.
Calculating observable properties of chemical systems is often classically intractable and widely viewed as a promising application of quantum information processing. Here, we introduce a new framework for solving generic quantum chemical dynamics problems using quantum logic. We experimentally demonstrate a proof-of-principle instance of our method using the QSCOUT ion-trap quantum computer, where we experimentally drive the ion-trap system to emulate the quantum wavepacket dynamics corresponding to the shared-proton within an anharmonic hydrogen bonded system. Following the experimental creation and propagation of the shared-proton wavepacket on the ion-trap, we extract measurement observables such as its time-dependent spatial projection and its characteristic vibrational frequencies to spectroscopic accuracy (3.3 cm –1 wavenumbers, corresponding to >99.9% fidelity). Our approach introduces a new paradigm for studying the chemical dynamics and vibrational spectra of molecules and opens the possibility to describe the behavior of complex molecular processes with unprecedented accuracy.
Quantum nuclear dynamics with wavepacket time evolution is classically intractable and viewed as a promising avenue for quantum information processing. Here, we use IonQ, Inc.'s 11-qubit trapped-ion quantum computer, Harmony, to study the quantum wavepacket dynamics of a shared-proton within a short-strong hydrogen-bonded system. We also provide the first application of distributed quantum computing for chemical dynamics problems, where a distributed set of quantum processes is constructed using a tensor network formalism. For a range of initial states, we experimentally drive the ion-trap system to emulate the quantum nuclear wavepacket as it evolves along the potential surface generated from the electronic structure. Following the experimental creation of the nuclear wavepacket, we extract measurement observables such as its time-dependent spatial projection and its characteristic vibrational frequencies to good agreement with classical results. Vibrational eigenenergies obtained from quantum computation are in agreement with those obtained from classical simulations to within a fraction of a kilocalorie per mole, thus suggesting chemical accuracy. Our approach opens a new paradigm for studying the quantum chemical dynamics and vibrational spectra of molecules and also provides the first demonstration of parallel quantum computation on a distributed set of ion-trap quantum computers.
The accurate computational study of wavepacket nuclear dynamics is considered to be a classically intractable problem, particularly with increasing dimensions. Here, we present two algorithms that, in conjunction with other methods developed by us, may result in one set of contributions for performing quantum nuclear dynamics in arbitrary dimensions. For one of the two algorithms discussed here, we present a direct map between the Born-Oppenheimer Hamiltonian describing the nuclear wavepacket time evolution and the control parameters of a spin-lattice Hamiltonian that describes the dynamics of qubit states in an ion-trap quantum computer. This map is exact for three qubits, and when implemented, the dynamics of the spin states emulates those of the nuclear wavepacket in a continuous representation. However, this map becomes approximate as the number of qubits grows. In a second algorithm, we present a general quantum circuit decomposition formalism for such problems using a method called the Quantum Shannon Decomposition. This algorithm is more robust and is exact for any number of qubits at the cost of increased circuit complexity. The resultant circuit is implemented on IBM's quantum simulator (QASM) for 3-7 qubits, without using a noise model so as to test the intrinsic accuracy of the method. In both cases, the wavepacket dynamics is found to be in good agreement with the classical propagation result and the corresponding vibrational frequencies obtained from the wavepacket density time evolution are in agreement to within a few tenths of a wavenumber.
Modern computational techniques used to simulate quantum chemistry are on the boundary of tractability due to the exponential growth of the molecular wavefunction, requiring a careful balance between molecule size and simulation accuracy. In recent years, quantum computing has risen in popularity as a potential alternative to conventional (classical) techniques; however, most methods rely on access to "digital" quantum computers composed of qubits and quantum gates, which at present are severely limited by noise. We have developed a real-time, analog approach to simulate vibronic chemical dynamics with existing quantum technology. Our approach uses an intuitive mapping of molecular electronic and vibrational degrees of freedom onto quantum resonators and qudit (d-level system) states, with controllable couplings between degrees of freedom. The measurement output can be mapped onto different time-dependent observables, including the time-domain simulation of vibronic spectra. Our approach can also incorporate controlled sources of noise to simulate system-bath interactions and dissipative dynamics at a minimal cost. We present experimental results using a trapped-ion device, thus showing the potential for near-term simulation of chemical dynamics in complex environments beyond the abilities of classical computers.
Quantum computers offer the potential to simulate chemical systems beyond the capabilities of classical computers. However, current quantum computing approaches to ab initio molecular dynamics (AIMD) and vibrational analysis largely rely on the Variational Quantum Eigensolver (VQE), whose circuit depth, iterative optimization, and measurement overhead hinder the practical simulation of molecular systems. Here, we extend Sample-based Quantum Diagonalization (SQD), a quantum sampling-based electronic-structure method, to AIMD and vibrational analysis on noisy quantum hardware. The resulting framework enables nuclear forces and Hessians to be derived from quantum-computed electronic energies, facilitating molecular dynamics and characterization of potential energy surfaces. We demonstrate the approach using diverse molecular processes, including H2 bond vibration, the proton-exchange reaction (H+ + H2), the bimolecular nucleophilic substitution (SN2) reaction (Cl- + CH3Cl), and proton-transfer dynamics between two water molecules involving transient formation of the Zundel cation (H2O···H+···OH2). Across these systems, SQD-AIMD trajectories and vibrational frequencies obtained with noisy quantum hardware/noise-models show excellent agreement with classical reference calculations and substantially improved accuracy relative to previously reported VQE-based simulations. Importantly, the SQD-based approach eliminates costly variational optimization and significantly reduces measurement requirements relative to VQE, enabling AIMD simulations spanning approximately 500 timesteps (∼200 fs), substantially longer than previously reported AIMD simulations on quantum hardware. These results establish SQD-AIMD and SQD-vibrational analysis as practical and scalable frameworks for simulating chemical reaction dynamics and elucidating reaction mechanisms on near-term quantum hardware, extending quantum computing applications beyond static electronic structure calculations.
Over the past years, the development of experimental techniques for the coherent manipulation and control of isolated quantum systems has made impressive progress. Such 'quantum-logic' methods are also highly attractive in a chemical context in view of unravelling and controlling the quantum dynamics of molecular collisions and chemical reactions. Quantum technologies have the potential to transform the way chemical dynamics are investigated - by providing highly sensitive methods for state readout and spectroscopy, by opening up new pathways for the quantum-state preparation of molecules and by enabling an improved control of their microscopic behavior on the single-particle level. However, for complex quantum systems like molecules, these techniques are still in their infancy and their considerable potential remains to be unlocked. The aim of the present research program supported by an Advanced Grant of the Swiss National Science Foundation is to merge the fields of quantum science and chemical dynamics by advancing quantum technologies to polyatomic molecular ions and by applying them to the study of ion-molecule collisions and chemical reactions. In this article, we review the salient experimental methods as well as prospects and challenges in the development of molecular quantum technologies and their applications to chemistry.
We present an approach based on tensor networks for distributed quantum computing simulation of chemical wavepacket dynamics in a continuous variable representation. The central idea is that the tensor-network representation of the multidimensional time-evolution operator naturally induces an elevated Hilbert space where the dynamics decomposes into a set of independent lower-dimensional propagations. This transformation converts an entangled quantum evolution into a set of parallel computational tasks that can be executed asynchronously across heterogeneous quantum and classical computing architectures. The resulting formalism establishes a direct connection between tensor-network decompositions, uniformly controlled quantum circuits, and asynchronous distributed quantum computing. The approach is developed with a goal towards hybrid quantum/classical implementation, and is appropriate for a general heterogeneous mixture of quantum hardware systems. The experimental realization of the asynchronously distributed quantum processes that arise from the tensor-network decomposition are carried out on the Sandia National Laboratories' trapped-ion quantum computer, where the circuits are compiled using native partial-entangling XX(θ) gates, reducing the expected two-qubit gate infidelity by more than 30\% relative to conventional fully entangling decompositions. We demonstrate the methodology by quantum computing the vibrational spectra of a small protonated water cluster that shows critical quantum nuclear behavior. Such water cluster systems have been found to be challenging for experimental action spectroscopy and for theory, and here, for the first time, we provide results for vibrational spectroscopy that are in agreement with the respective classical results to within 4cm−1, thus allowing for the potential for spectroscopic accuracy from quantum computations.