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The Journal of Physical Chemistry Letters

Quantum Algorithm for Full Configuration Interaction Calculations without Controlled Time Evolutions

Kenji Sugisaki, Chikako Sakai, Kazuo Toyota, Kazunobu Sato, Daisuke Shiomi, Takeji Takui

Published Nov 8, 2021• 16 citations
Publisher

Abstract

A quantum phase estimation algorithm allows us to perform full configuration interaction (full-CI) calculations on quantum computers with polynomial costs against the system size under study, but it requires quantum simulation of the time evolution of the wave function conditional on an ancillary qubit, which makes the algorithm implementation on real quantum devices difficult. Here, we discuss an application of the Bayesian phase difference estimation algorithm that is free from controlled time evolution operations to the full-CI calculations.

DOI
10.1021/acs.jpclett.1c03214

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A quantum phase estimation algorithm allows us to perform full configuration interaction (full-CI) calculations on quantum computers with polynomial costs against the system size under study, but it requires quantum simulation of the time evolution of the wave function conditional on an ancillary qubit, which makes the algorithm implementation on real quantum devices difficult. Here, we discuss an application of the Bayesian phase difference estimation algorithm that is free from controlled time evolution operations to the full-CI calculations.
Quantum computers can perform full configuration interaction (full-CI) calculations by utilising the quantum phase estimation (QPE) algorithms including Bayesian phase estimation (BPE) and iterative quantum phase estimation (IQPE). In these quantum algorithms, the time evolution of wave functions for atoms and molecules is simulated conditionally with an ancillary qubit as the control, which make implementation to real quantum devices difficult. Also, most of the problems in chemistry discuss energy differences between two electronic states rather than total energies themselves, and thus direct calculations of energy gaps are promising for future applications of quantum computers to real chemistry problems. In the race of finding efficient quantum algorithms to solve quantum chemistry problems, we test a Bayesian phase difference estimation (BPDE) algorithm, which is a general algorithm to calculate the difference of two eigenphases of unitary operators in the several cases of the direct calculations of energy gaps between two electronic states on quantum computers, including vertical ionisation energies, singlet-triplet energy gaps, and vertical excitation energies. In the BPDE algorithm, state preparation is carried out conditionally on the ancillary qubit, and the time evolution of the wave functions in superposition of two electronic states are executed unconditionally. Based on our test, we conclude that BPDE is capable of computing the energy gap with an accuracy similar to BPE without controlled-time evolution simulations and with the smaller number of iterations in Bayesian optimisations.
The full configuration interaction (full-CI) method is capable of providing the numerically best wave functions and energies of atoms and molecules within basis sets being used, although it is intractable for classical computers. Quantum computers can perform full-CI calculations in polynomial time against the system size by adopting a quantum phase estimation algorithm (QPEA). In the QPEA, the preparation of initial guess wave functions having sufficiently large overlap with the exact wave function is recommended. The Hartree-Fock (HF) wave function is a good initial guess only for closed shell singlet molecules and high-spin molecules carrying no spin-β unpaired electrons, around their equilibrium geometry, and thus, the construction of multiconfigurational wave functions without performing post-HF calculations on classical computers is highly desired for applying the method to a wide variety of chemistries and physics. In this work, we propose a method to construct multiconfigurational initial guess wave functions suitable for QPEA-based full-CI calculations on quantum computers, by utilizing diradical characters computed from spin-projected UHF wave functions. The proposed approach drastically improves the wave function overlap, particularly in molecules with intermediate diradical characters.
High Resolution Image Download MS PowerPoint Slide A Bayesian phase difference estimation (BPDE) algorithm allows us to compute the energy gap of two electronic states of a given Hamiltonian directly by utilizing the quantum superposition of their wave functions. Here we report an extension of the BPDE algorithm to the direct calculation of the energy difference of two molecular geometries. We apply the BPDE algorithm for the calculation of numerical energy gradients based on the two-point finite-difference method, enabling us to execute geometry optimization of one-dimensional molecules at the full-CI level on a quantum computer. Results of numerical quantum circuit simulations of the geometry optimization of the H 2 molecule with the STO-3G and 6-31G basis sets, the LiH and BeH 2 molecules at the full-CI/STO-3G level, and the N 2 molecule at the CASCI(6e,6o)/6-311G* level are given.
Quantum computers are capable to efficiently perform full configuration interaction (FCI) calculations of atoms and molecules by using the quantum phase estimation (QPE) algorithm. Because the success probability of the QPE depends on the overlap between approximate and exact wave functions, efficient methods to prepare accurate initial guess wave functions enough to have sufficiently large overlap with the exact ones are highly desired. Here, we propose a quantum algorithm to construct the wave function consisting of one configuration state function, which is suitable for the initial guess wave function in QPE-based FCI calculations of open-shell molecules, based on the addition theorem of angular momentum. The proposed quantum algorithm enables us to prepare the wave function consisting of an exponential number of Slater determinants only by a polynomial number of quantum operations.
Phase estimation is known to be a robust method for single-qubit gate calibration in quantum computers, while Bayesian estimation is widely used in devising optimal methods for learning in quantum systems. We present a Bayesian method that adaptively chooses a control phase and the time of coherent evolution. The uniqueness of the approach is to use analytics to implement an efficient numerical algorithm that offers exact calculation of the Bayesian probability and associated utility functions, even in the presence of noise. We determine the utility of control parameter values using functions of the prior probability of the phase that quantify expected knowledge gain in terms of either expected narrowing of the posterior or expected information gain. We find that by maximizing the of expected gain we obtain phase estimates having standard deviation a factor of 1.43 larger than the Heisenberg limit using a classical sequential strategy for noise-free experiments. In the presence of dephasing, we find near-optimal performance with respect to the Cramér-Rao bound. We also demonstrate some robustness of the estimates to noise that is not accounted for in the model of the estimator, making the methods suitable for calibrating operations in quantum computers. The rate of gain can be adjusted to account for times in the experiment other than the coherent evolution of the unknown phase, such as times required for state preparation or readout. The combined features of the method make it well suited to single-qubit gate calibration in trapped-ion or neutral atom experiments and promises a wide range of other applications by offering near-optimal phase estimation that straightforwardly accounts for experimental imperfections.
The phase estimation algorithm is a powerful quantum algorithm with applications in cryptography, number theory, and simulation of quantum systems. We use this algorithm to simulate the time evolution of a system of two spin-1/2 particles under a Heisenberg Hamiltonian. The evolution is performed through both classical simulations of quantum computers and real quantum computers via IBM's Qiskit platform. We also introduce three optimizations to the algorithm: circular, iterative, and Bayesian. We apply these optimizations to our simulations and investigate how the performance improves. We also discuss the paradigms of iterative and update-based algorithms, which are attributes of these optimizations that can improve quantum algorithms generally.