# Publications

## 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.

## 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 H_{2}O^{+} 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.

## 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.

## 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.

## Molecular Structure Optimization based on Electrons-Nuclei Quantum Dynamics Computation

A new concept of the molecular structure optimization method based on quantum dynamics computations is presented. Nuclei are treated as quantum mechanical particles, as are electrons, and the many-body wave function of the system is optimized by the imaginary time evolution method. A demonstration with a 2-dimensional H_{2}^{+ }molecule shows that the optimized nuclear positions can be specified with a small number of observations. This method is considered to be suitable for quantum computers, the development of which will realize its application as a powerful method.

## Calculating the Green's function of two-site Fermionic Hubbard model in a photonic system

The Green's function has been an indispensable tool to study many-body systems that remain one of the biggest challenges in modern quantum physics for decades. The complicated calculation of Green's function impedes the research of many-body systems. The appearance of the noisy intermediate-scale quantum devices and quantum-classical hybrid algorithm inspire a new method to calculate Green's function. Here we design a programmable quantum circuit for photons with utilizing the polarization and the path degrees of freedom to construct a highly-precise variational quantum state of a photon, and first report the experimental realization for calculating the Green's function of the two-site Fermionic Hubbard model, a prototypical model for strongly-correlated materials, in photonic systems. We run the variational quantum eigensolver to obtain the ground state and excited states of the model, and then evaluate the transition amplitudes among the eigenstates. The experimental results present the spectral function of Green's function, which agrees well with the exact results. Our demonstration provides the further possibility of the photonic system in quantum simulation and applications in solving complicated problems in many-body systems, biological science, and so on.

## Deep variational quantum eigensolver for excited states and its application to quantum chemistry calculation of periodic materials

A programmable quantum device that has a large number of qubits without fault-tolerance has emerged recently. Variational Quantum Eigensolver (VQE) is one of the most promising ways to utilize the computational power of such devices to solve problems in condensed matter physics and quantum chemistry. As the size of the current quantum devices is still not large for rivaling classical computers at solving practical problems, Fujii et al. proposed a method called "Deep VQE" which can provide the ground state of a given quantum system with the smaller number of qubits by combining the VQE and the technique of coarse-graining [K. Fujii, et al, arXiv:2007.10917]. In this paper, we extend the original proposal of Deep VQE to obtain the excited states and apply it to quantum chemistry calculation of a periodic material, which is one of the most impactful applications of the VQE. We first propose a modified scheme to construct quantum states for coarse-graining in Deep VQE to obtain the excited states. We also present a method to avoid a problem of meaningless eigenvalues in the original Deep VQE without restricting variational quantum states. Finally, we classically simulate our modified Deep VQE for quantum chemistry calculation of a periodic hydrogen chain as a typical periodic material. Our method reproduces the ground-state energy and the first-excited-state energy with the errors up to O(1)% despite the decrease in the number of qubits required for the calculation by two or four compared with the naive VQE. Our result will serve as a beacon for tackling quantum chemistry problems with classically-intractable sizes by smaller quantum devices in the near future.

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