Computational analysis of chemical reactions using a variational quantum eigensolver algorithm without specifying spin multiplicity

The analysis of a chemical reaction along the ground state potential energy surface in conjunction with an unknown spin state is challenging because electronic states must be separately computed several times using different spin multiplicities to find the lowest energy state. However, in principle, the ground state could be obtained with just a single calculation using a quantum computer without specifying the spin multiplicity in advance. In the present work, ground state potential energy curves for PtCO were calculated as a proof-of-concept using a variational quantum eigensolver (VQE) algorithm. This system exhibits a singlet-triplet crossover as a consequence of the interaction between Pt and CO. VQE calculations using a statevector simulator were found to converge to a singlet state in the bonding region, while a triplet state was obtained at the dissociation limit. Calculations performed using an actual quantum device provided potential energies within ±2 kcal/mol of the simulated energies after adopting error mitigation techniques. The spin multiplicities in the bonding and dissociation regions could be clearly distinguished even in the case of a small number of shots. The results of this study suggest that quantum computing can be a powerful tool for the analysis of the chemical reactions of systems for which the spin multiplicity of the ground state and variations in this parameter are not known in advance.


Quantum chemistryNISQ deviceJoint research
Soichi Shirai, Hokuto Iwakiri, Keita Kanno, Takahiro Horiba, Keita Omiya, Hirotoshi Hirai, Sho Koh

Quantum-Selected Configuration Interaction: classical diagonalization of Hamiltonians in subspaces selected by quantum computers

We propose quantum-selected configuration interaction (QSCI), a class of hybrid quantum-classical algorithms for calculating the ground- and excited-state energies of many-electron Hamiltonians on noisy quantum devices. Suppose that an approximate ground state can be prepared on a quantum computer either by variational quantum eigensolver or by some other method. Then, by sampling the state in the computational basis, which is hard for classical computation in general, one can identify the electron configurations that are important for reproducing the ground state. The Hamiltonian in the subspace spanned by those important configurations is diagonalized on classical computers to output the ground-state energy and the corresponding eigenvector. The excited-state energies can be obtained similarly. The result is robust against statistical and physical errors because the noisy quantum devices are used only to define the subspace, and the resulting ground-state energy strictly satisfies the variational principle even in the presence of such errors. The expectation values of various other operators can also be estimated for obtained eigenstates with no additional quantum cost, since the explicit eigenvectors in the subspaces are known. We verified our proposal by numerical simulations, and demonstrated it on a quantum device for an 8-qubit molecular Hamiltonian. The proposed algorithms are potentially feasible to tackle some challenging molecules by exploiting quantum devices with several tens of qubits, assisted by high-performance classical computing resources for diagonalization.


Quantum chemistryMaterial scienceNISQ device
Keita Kanno, Masaya Kohda, Ryosuke Imai, Sho Koh, Kosuke Mitarai, Wataru Mizukami, Yuya O. Nakagawa

Almost optimal measurement scheduling of molecular Hamiltonian via finite projective plane

We propose an efficient and almost optimal scheme for measuring molecular Hamiltonians in quantum chemistry on quantum computers, which requires 2N2 distinct measurements in the leading order with N being the number of molecular orbitals. It achieves the state-of-the-art by improving a previous proposal by Bonet-Monroig et al. [Phys. Rev. X 10, 031064 (2020)] which exhibits 17N2/6 scaling in the leading order. We develop a novel method based on a finite projective plane to construct sets of simultaneously-measurable operators contained in molecular Hamiltonians. Each measurement only requires a depth-O(N) circuit consisting of O(N2) one- and two-qubit gates under the Jordan-Wigner and parity mapping, assuming the linear connectivity of qubits on quantum hardwares. Because evaluating expectation values of molecular Hamiltonians is one of the major bottlenecks in the applications of quantum devices to quantum chemistry, our finding is expected to accelerate such applications.


NISQ deviceQuantum chemistry
Wataru Inoue, Koki Aoyama, Yusuke Teranishi, Keita Kanno, Yuya O. Nakagawa, Kosuke Mitarai

Clifford+T-gate Decomposition with Limited Number of T gates, its Error Analysis, and Performance of Unitary Coupled Cluster Ansatz in Pre-FTQC Era

Fault-tolerant quantum computation (FTQC) is essential to robustly implement quantum algorithms and thus to maximize advantages of quantum computers. In this context, a quantum circuit is decomposed into universal gates that can be fault-tolerantly implemented, for example, Clifford+T gates. Here, T gate is usually regarded as an essential resource for quantum computation because its action cannot be simulated efficiently on classical computers. Practically, it is highly likely that only a limited number of T gates are available in the near future due to its experimental difficulty of fault-tolerant implementation. In this paper, considering this Pre-FTQC era, we investigate Clifford+T decomposition with a limited budget of T gates and propose a new model of the error of such decomposition. More concretely, we propose an algorithm to generate the most accurate Clifford+T-gate decomposition of a given single-qubit rotation gate with a fixed number of T gates. We also propose to model the error of Clifford+T decomposition using well-known depolarizing noise by considering the average of the effects of the error. We numerically verified our model successfully explains the decomposition error for a wide variety of molecules using our decomposition algorithm. Thus, we shed light on a first-stage application of quantum computers from a practical point of view and fuel further research towards what quantum computation can achieve in the upcoming future.


Quantum chemistryNISQ deviceFault-tolerant quantum computer
Kohdai Kuroiwa, Yuya O. Nakagawa

Quantum Car-Parrinello Molecular Dynamics: A Cost-Efficient Molecular Simulation Method on Near-Term Quantum Computers

In this paper, we propose a cost-reduced method for finite-temperature molecular dynamics on a near-term quantum computer, Quantum Car-Parrinello molecular dynamics (QCPMD). One of the most promising applications of near-term quantum computers is quantum chemistry. It has been expected that simulations of molecules via molecular dynamics can be also efficiently performed on near-term quantum computers by applying a promising near-term quantum algorithm of the variational quantum eigensolver (VQE). However, this method may demand considerable computational costs to achieve a sufficient accuracy, and otherwise, statistical noise can significantly affect the results. To resolve these problems, we invent an efficient method for molecular time evolution inspired by Car-Parrinello method. In our method, parameters characterizing the quantum state evolve based on equations of motion instead of being optimized. Furthermore, by considering Langevin dynamics, we can make use of the intrinsic statistical noise. As an application of QCPMD, we propose an efficient method for vibrational frequency analysis of molecules in which we can use the results of the molecular dynamics calculated by QCPMD. Numerical experiments show that our method can precisely simulate the Langevin dynamics at the equilibrium state, and we can successfully predict a given molecule's eigen frequencies. Furthermore, in the numerical simulation, our method achieves a substantial cost reduction compared with molecular dynamics using the VQE. Our method achieves an efficient computation without using widely employed method of the VQE. In this sense, we open up a new possibility of molecular dynamics on near-term quantum computers. We expect our results inspire further invention of efficient near-term quantum algorithms for simulation of molecules.


NISQ deviceJoint researchQuantum chemistry
Kohdai Kuroiwa, Takahiro Ohkuma, Hirokazu Sato, Ryosuke Imai

Analytical formulation of the second-order derivative of energy for orbital-optimized variational quantum eigensolver: application to polarizability

We develop a quantum-classical hybrid algorithm to calculate the analytical second-order derivative of the energy for the orbital-optimized variational quantum eigensolver (OO-VQE), which is a method to calculate eigenenergies of a given molecular Hamiltonian by utilizing near-term quantum computers and classical computers. We show that all quantities required in the algorithm to calculate the derivative can be evaluated on quantum computers as standard quantum expectation values without using any ancillary qubits. We validate our formula by numerical simulations of quantum circuits for computing the polarizability of the water molecule, which is the second-order derivative of the energy with respect to the electric field. Moreover, the polarizabilities and refractive indices of thiophene and furan molecules are calculated as a testbed for possible industrial applications. We finally analyze the error-scaling of the estimated polarizabilities obtained by the proposed analytical derivative versus the numerical one obtained by the finite difference. Numerical calculations suggest that our analytical derivative may require fewer measurements (runs) on quantum computers than the numerical derivative to achieve the same fixed accuracy.


Quantum chemistryNISQ deviceJoint research
Yuya O. Nakagawa, Jiabao Chen, Shotaro Sudo, Yu-ya Ohnishi, Wataru Mizukami

Quantum expectation value estimation by computational basis sampling

Measuring expectation values of observables is an essential ingredient in variational quantum algorithms. A practical obstacle is the necessity of a large number of measurements for statistical convergence to meet requirements of precision, such as chemical accuracy in the application to quantum chemistry computations. Here we propose an algorithm to estimate the expectation value based on its approximate expression as a weighted sum of classically-tractable matrix elements with some modulation, where the weight and modulation factors are evaluated by sampling appropriately prepared quantum states in the computational basis on quantum computers. Our algorithm is expected to require fewer measurements than conventional methods for a required statistical precision of the expectation value when a target quantum state is concentrated in particular computational basis states. We provide numerical comparisons of our method with existing ones for measuring electronic ground state energies (expectation values of electronic Hamiltonians for the lowest-energy states) of various small molecules. Numerical results show that our method can reduce the numbers of measurements to obtain the ground state energies for a targeted precision by several orders of magnitudes for molecules whose ground states are concentrated. Our results provide another route to measure expectation values of observables, which could accelerate the variational quantum algorithms.


Quantum chemistry
by Masaya Kohda, Ryosuke Imai, Keita Kanno, Kosuke Mitarai, Wataru Mizukami, Yuya O. Nakagawa

Non-adiabatic Quantum Wavepacket Dynamics Simulation Based on Electronic Structure Calculations using the Variational Quantum Eigensolver

A non-adiabatic nuclear wavepacket dynamics simulation of the H2O+ de-excitation process is performed based on electronic structure calculations using the variational quantum eigensolver. The adiabatic potential energy surfaces and non-adiabatic coupling vectors are computed with algorithms for noisy intermediate-scale quantum devices, and time propagation is simulated with conventional methods for classical computers. The results of non-adiabatic transition dynamics from the B~ state to A~ state reproduce the trend reported in previous studies, which suggests that this quantum-classical hybrid scheme may be a useful application for noisy intermediate-scale quantum devices.


Quantum chemistryNISQ deviceJoint research
by Hirotoshi Hirai, Sho Koh

Analytic energy gradient for state-averaged orbital-optimized variational quantum eigensolvers and its application to a photochemical reaction

Elucidating photochemical reactions is vital to understand various biochemical phenomena and develop functional materials such as artificial photosynthesis and organic solar cells, albeit its notorious difficulty by both experiments and theories. The best theoretical way so far to analyze photochemical reactions at the level of ab initio electronic structure is the state-averaged multi-configurational self-consistent field (SA-MCSCF) method. However, the exponential computational cost of classical computers with the increasing number of molecular orbitals hinders applications of SA-MCSCF for large systems we are interested in. Utilizing quantum computers was recently proposed as a promising approach to overcome such computational cost, dubbed as SA orbital-optimized variational quantum eigensolver (SA-OO-VQE). Here we extend a theory of SA-OO-VQE so that analytical gradients of energy can be evaluated by standard techniques that are feasible with near-term quantum computers. The analytical gradients, known only for the state-specific OO-VQE in previous studies, allow us to determine various characteristics of photochemical reactions such as the minimal energy (ME) points and the conical intersection (CI) points. We perform a proof-of-principle calculation of our methods by applying it to the photochemical cis-trans isomerization of 1,3,3,3-tetrafluoropropene. Numerical simulations of quantum circuits and measurements can correctly capture the photochemical reaction pathway of this model system, including the ME and CI points. Our results illustrate the possibility of leveraging quantum computers for studying photochemical reactions.


Quantum chemistryNISQ deviceJoint research
by Keita Arimitsu, Yuya O. Nakagawa, Sho Koh, Wataru Mizukami, Qi Gao, Takao Kobayashi

Non-normal Hamiltonian dynamics in quantum systems and its realization on quantum computers

The eigenspectrum of a non-normal matrix, which does not commute with its Hermitian conjugate, is a central issue of non-Hermitian physics that has been extensively studied in the past few years. There is, however, another characteristic of a non-normal matrix that has often been overlooked: the pseudospectrum, or the set of spectra under small perturbations. In this paper, we study the dynamics driven by the non-normal matrix (Hamiltonian) realized as a continuous quantum trajectory of the Lindblad master equation in open quantum systems and point out that the dynamics can reveal the nature of unconventional pseudospectrum of the non-normal Hamiltonian. In particular, we focus on the transient dynamics of the norm of an unnormalized quantum state evolved with the non-normal Hamiltonian, which is related to the probability for observing the trajectory with no quantum jump. We formulate the transient suppression of the decay rate of the norm due to the pseudospectral behavior and derive a non-Hermitian/non-normal analog of the time-energy uncertainty relation. We also consider two methods to experimentally realize the non-normal dynamics and observe our theoretical findings on quantum computers: one uses a technique to realize non-unitary operations on quantum circuits and the other leverages a quantum-classical hybrid algorithm called variational quantum simulation. Our demonstrations using cloud-based quantum computers provided by IBM Quantum exhibit the frozen dynamics of the norm in transient time, which can be regarded as a non-normal analog of the quantum Zeno effect.


Quantum chemistryCondensed matter physicsNISQ deviceJoint research
by Nobuyuki Okuma, Yuya O. Nakagawa