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 {it 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.
The Greens 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 Greens function impedes the research of many-body systems. T
he appearance of the noisy intermediate-scale quantum devices and quantum-classical hybrid algorithm inspire a new method to calculate Greens 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 Greens 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 Greens 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.
The variational quantum eigensolver (VQE) is a promising algorithm to compute eigenstates and eigenenergies of a given quantum system that can be performed on a near-term quantum computer. Obtaining eigenstates and eigenenergies in a specific symmetr
y sector of the system is often necessary for practical applications of the VQE in various fields ranging from high energy physics to quantum chemistry. It is common to add a penalty term in the cost function of the VQE to calculate such a symmetry-resolving energy spectrum, but systematic analysis on the effect of the penalty term has been lacking, and the use of the penalty term in the VQE has not been justified rigorously. In this work, we investigate two major types of penalty terms for the VQE that were proposed in the previous studies. We show a penalty term in one of the two types works properly in that eigenstates obtained by the VQE with the penalty term reside in the desired symmetry sector. We further give a convenient formula to determine the magnitude of the penalty term, which may lead to the faster convergence of the VQE. Meanwhile, we prove that the other type of penalty terms does not work for obtaining the target state with the desired symmetry in a rigorous sense and even gives completely wrong results in some cases. We finally provide numerical simulations to validate our analysis. Our results apply to general quantum systems and lay the theoretical foundation for the use of the VQE with the penalty terms to obtain the symmetry-resolving energy spectrum of the system, which fuels the application of a near-term quantum computer.
We present a quantum-classical hybrid algorithm that simulates electronic structures of periodic systems such as ground states and quasiparticle band structures. By extending the unitary coupled cluster (UCC) theory to describe crystals in arbitrary
dimensions, we numerically demonstrate in hydrogen chain that the UCC ansatz implemented on a quantum circuit can be successfully optimized with a small deviation from the exact diagonalization over the entire range of the potential energy curves. Furthermore, with the aid of the quantum subspace expansion method, in which we truncate the Hilbert space within the linear response regime from the ground state, the quasiparticle band structure is computed as charged excited states. Our work establishes a powerful interface between the rapidly developing quantum technology and modern material science.
We propose an orbital optimized method for unitary coupled cluster theory (OO-UCC) within the variational quantum eigensolver (VQE) framework for quantum computers. OO-UCC variationally determines the coupled cluster amplitudes and also molecular orb
ital coefficients. Owing to its fully variational nature, first-order properties are readily available. This feature allows the optimization of molecular structures in VQE without solving any additional equations. Furthermore, the method requires smaller active space and shallower quantum circuit than UCC to achieve the same accuracy. We present numerical examples of OO-UCC using quantum simulators, which include the geometry optimization of the water and ammonia molecules using analytical first derivatives of the VQE.
We calculate in detail the Renyi entanglement entropies of cTPQ states as a function of subsystem volume, filling the details of our prior work [Nature Communications 9, 1635 (2018)], where the formulas were first presented. Working in a limit of lar
ge total volume, we find universal formulas for the Renyi entanglement entropies in a region where the subsystem volume is comparable to that of the total system. The formulas are applicable to the infinite temperature limit as well as general interacting systems. For example we find that the second Renyi entropy of cTPQ states in terms of subsystem volume is written universally up to two constants, $S_2(ell)=-ln K(beta)+ellln a(beta)-lnleft(1+a(beta)^{-L+2ell}right)$, where $L$ is the total volume of the system and $a$ and $K$ are two undetermined constants. The uses of the formulas were already presented in our prior work and we mostly concentrate on the theoretical aspect of the formulas themselves. Aside from deriving the formulas for the Renyi Page curves, the expression for the von Neumann Page curve is also derived, which was not presented in our previous work.
We propose that the properties of the capacity of entanglement (COE) in gapless systems can efficiently be investigated through the use of the distribution of eigenvalues of the reduced density matrix (RDM). The COE is defined as the fictitious heat
capacity calculated from the entanglement spectrum. Its dependence on the fictitious temperature can reflect the low-temperature behavior of the physical heat capacity, and thus provide a useful probe of gapless bulk or edge excitations of the system. Assuming a power-law scaling of the COE with an exponent $alpha$ at low fictitious temperatures, we derive an analytical formula for the distribution function of the RDM eigenvalues. We numerically test the effectiveness of the formula in relativistic free scalar boson in two spatial dimensions, and find that the distribution function can detect the expected $alpha=3$ scaling of the COE much more efficiently than the raw data of the COE. We also calculate the distribution function in the ground state of the half-filled Landau level with short-range interactions, and find a better agreement with the $alpha=2/3$ formula than with the $alpha=1$ one, which indicates a non-Fermi-liquid nature of the system.
Correlated many-body problems ubiquitously appear in various fields of physics such as condensed matter physics, nuclear physics, and statistical physics. However, due to the interplay of the large number of degrees of freedom, it is generically impo
ssible to treat these problems from first principles. Thus the construction of a proper model, namely effective Hamiltonian, is essential. Here, we propose a simple scheme of constructing Hamiltonians from given energy or entanglement spectra with machine learning. We apply the proposed scheme to the Hubbard model at the half-filling, and compare the obtained effective low-energy spin-1/2 model with several analytic results based on the high order perturbation theory which have been inconsistent with each other. We also show that our approach can be used to construct the entanglement Hamiltonian of a quantum many-body state from its entanglement spectrum as well. We exemplify this using the ground states of the $S=1/2$ two-leg Heisenberg ladders. We observe a qualitative difference between the entanglement Hamiltonians of the two phases (the Haldane phase and the Rung Singlet phase) of the model due to the different origin of the entanglement. In the Haldane phase, we find that the entanglement Hamiltonian is non-local by nature, and the locality can be restored by introducing the anisotropy and turning the system into the large-$D$ phase. Possible applications to the study of strongly-correlated systems and the model construction from experimental data are discussed.
