Excited states of molecules lie in the heart of photochemistry and chemical reactions. The recent development in quantum computational chemistry leads to inventions of a variety of algorithms that calculate the excited states of molecules on near-term quantum computers, but they require more computational burdens than the algorithms for calculating the ground states. In this study, we propose a scheme of supervised quantum machine learning which predicts the excited-state properties of molecules only from their ground state wavefunction resulting in reducing the computational cost for calculating the excited states. Our model is comprised of a quantum reservoir and a classical machine learning unit which processes the measurement results of single-qubit Pauli operators with the output state from the reservoir. The quantum reservoir effectively transforms the single-qubit operators into complicated multi-qubit ones which contain essential information of the system, so that the classical machine learning unit may decode them appropriately. The number of runs for quantum computers is saved by training only the classical machine learning unit, and the whole model requires modest resources of quantum hardware that may be implemented in current experiments. We illustrate the predictive ability of our model by numerical simulations for small molecules with and without noise inevitable in near-term quantum computers. The results show that our scheme well reproduces the first and second excitation energies as well as the transition dipole moment between the ground states and excited states only from the ground state as an input. We expect our contribution will enhance the applications of quantum computers in the study of quantum chemistry and quantum materials.
Probing the real time dynamics of a reacting molecule remains one of the central challenges in chemistry. In this letter we show how the time-dependent wavefunction of an excited-state reacting molecule can be completely reconstructed from resonant coherent anti-Stokes Raman spectroscopy. The method assumes knowledge of the ground-state potential but not of any excited-state potential, although we show that the latter can be computed once the time-dependent excited-state wavefunction is known. The formulation applies to polyatomics as well as diatomics and to bound as well as dissociative exci…
We demonstrate that, if a truncated expansion of a wave function is small, then the standard excited states computational method, of optimizing one root of a secular equation, may lead to an incorrect wave function - despite the correct energy according to the theorem of Hylleraas, Undheim and McDonald - whereas our proposed method [J. Comput. Meth. Sci. Eng. 8, 277 (2008)] (independent of orthogonality to lower lying approximants) leads to correct reliable small truncated wave functions. The demonstration is done in He excited states, using truncated series expansions in Hylleraas coordinates…
In this paper we design and use two Deep Learning models to generate the ground and excited wavefunctions of different Hamiltonians suitable for the study the vibrations of molecular systems. The generated neural networks are trained with Hamiltonians that have analytical solutions, and ask the network to generalize these solutions to more complex Hamiltonian functions. This approach allows to reproduce the excited vibrational wavefunctions of different molecular potentials. All methodologies used here are data-driven, therefore they do not assume any information about the underlying physical …
Ab initio electronic excited state calculations are necessary for the quantitative study of photochemical reactions, but their accurate computation on classical computers is plagued by prohibitive scaling. The Variational Quantum Deflation (VQD) is an extension of the Variational Quantum Eigensolver (VQE) for calculating electronic excited state energies, and has the potential to address some of these scaling challenges using quantum computers. However, quantum computers available in the near term can only support a limited number of circuit operations, so reducing the quantum computational co…
We introduce a unitary coupled-cluster (UCC) ansatz termed $k$-UpCCGSD that is based on a family of sparse generalized doubles (D) operators which provides an affordable and systematically improvable unitary coupled-cluster wavefunction suitable for implementation on a near-term quantum computer. $k$-UpCCGSD employs $k$ products of the exponential of pair coupled-cluster double excitation operators (pCCD), together with generalized single (S) excitation operators. We compare its performance in both efficiency of implementation and accuracy with that of the generalized UCC ansatz employing the …
In this paper [published in Phys. Rev. E 102, 042210 (2020)], a new method for the calculation of excited chaotic eigenfunctions in arbitrary energy windows is presented. We demonstrate the feasibility of using wavefunctions localized on unstable periodic orbits as efficient basis sets for this task in classically chaotic systems. The number of required localized wavefunctions is only of the order of the ratio t H /t E , with t H the Heisenberg time and t E the Ehrenfest time. As an illustration, we present convincing results for a coupled two-dimensional quartic oscillator with chaotic dynami…
For a system with interacting quantum mechanical particles in a one-dimensional harmonic oscillator, a trial wavefunction with simple structure based on the solution of the corresponding two-particle system is suggested and tested numerically. With the inclusion of a scaling parameter for the distance between particles, at least for the very small systems tested here the ansatz gives a very good estimate of the ground state energy, with the error being of the order of ~1% of the gap to the first excited state.
The Born rule, which is one of foundational axioms of quantum theory, states that the probability of obtain outcome $a$ for the quantum state $|ψ\rangle$ is determined by $P(a)=|\langle a|ψ\rangle|^{2}$. Despite its great success in predicting the experimental outcomes, there still lacks a direct way to verify the Born rule. Here, we show that the weak value based direct measurement of superposition wavefunction is feasible, which can be used to verify the Born rule directly. The plausible experiment is suggested.
We use a simple Hubbard model to characterize the electronic excited states of the dibenzoterrylene (DBT) molecule; we compute the excited state transition energies and oscillator strengths from the ground state to several singlet excited states. We consider the lowest singlet and triplet states of the molecule, examine their wavefunctions, and compute the density correlation functions that describe these states. We find that the DBT ground state is mostly a closed shell singlet with very slight radical character. We predict a relatively small singlet-triplet splitting of 0.75 eV, which is les…
For a given many-electron molecule, it is possible to define a corresponding one-electron Schrödinger equation, using potentials derived from simple atomic densities, whose solution predicts fairly accurate molecular orbitals for single- and multi-determinant wavefunctions for the molecule. The energy is not predicted and must be evaluated by calculating Coulomb and exchange interactions over the predicted orbitals. Transferable potentials for first-row atoms and transition metal oxides that can be used without modification in different molecules are reported. For improved accuracy, molecular …
The maturation of analytical derivative theory over the past few decades has enabled classical electronic structure theory to provide accurate and efficient predictions of a wide variety of observable properties. However, classical implementations of analytical derivative theory take advantage of explicit computational access to the approximate electronic wavefunctions in question, which is not possible for the emerging case of hybrid quantum/classical methods. Here, we develop an efficient Lagrangian-based approach for analytical first derivatives of hybrid quantum/classical methods using onl…
In this paper we present a model for the electronic excited states of $π$ conjugated -acene molecules such as tetracene, pentacene, and hexacene. We use a simple Hubbard model with a limited basis to describe the low lying excitations with reasonable quantitative accuracy. We are able to produce semi-analytic wavefunctions for the electronic states of the system, which allows us to compute the density correlation functions for various states such as the ground state, the first two singly excited states, and the lowest lying doubly excited state. We show that in this lowest lying doubly excited…
We build the first analytic empirical potential for the most deeply bound $\mbox{Li}_{2}$ state: $b\left(1^{3}Π_{u}\right)$. Our potential is based on experimental energy transitions covering $v=0-34$, and very high precision theoretical long-range constants. It provides high accuracy predictions up to $v=100$ which pave the way for high-precision long-range measurements, and hopefully an eventual resolution of the age old discrepancy between experiment and theory for the $\mbox{Li}\left(2^{2}S\right)+\mbox{Li}\left(2^{2}P\right)$ $C_{3}$ value. State of the art ab initio calculations predict …
In this communication, we propose a method for obtaining isolated excited states within the Full Configuration Interaction Quantum Monte Carlo framework. This method allows for stable sampling with respect to collapse to lower energy states and requires no uncontrolled approximations. In contrast with most previous methods to extract excited state information from Quantum Monte Carlo methods, this results from a modification to the underlying propagator, and does not require explicit orthogonalization, analytic continuation, transient estimators or restriction of the Hilbert space via a trial …
Quantum simulations with ultracold atoms typically create atomic wavefunctions with structures at optical length scales, where direct imaging suffers from the diffraction limit. In analogy to advances in optical microscopy for biological applications, we use a non-linear atomic response to surpass the diffraction limit. Exploiting quantum interference, we demonstrate imaging with super-resolution of $λ/100$ and excellent temporal resolution of 500 ns. We characterize our microscope's performance by measuring the ensemble averaged wavefunction of atoms within the unit cells of an optical lattic…
We propose a scheme for universal quantum computing based on Kramers rare-earth ions. Their nuclear spins in the presence of a Zeeman-split electronic crystal field ground state act as 'passive' qubits which store quantum information. The qubits can be activated optically by fast coherent transitions to excited crystal field states with a magnetic moment. The dipole interaction between these states is used to implement CNOT gates. We compare our proposal with a similar one based on phosphorus donor atoms in silicon and discuss the significantly improved CNOT gate time as compared to rare-earth…
We present a comprehensive theory for interrogation of the quantum state of a two-level system (TLS) based on a free-electron - bound-electron resonant interaction scheme. The scheme is based on free electrons, whose quantum electron wavefunction is pre-shaped or optically modulated by lasers in an electron microscope setup and then inelastically scattered by a quantum TLS target (e.g., atom, quantum dot, crystal defect center, etc.) upon traversing in proximity to the target. Measurement of the post-interaction energy spectrum of the electrons, probes and quantifies the full Bloch sphere para…
Two-photon photoassociation of hot magnesium atoms by femtosecond laser pulses, creating electronically excited magnesium dimer molecules, is studied from first principles, combining \textit{ab initio} quantum chemistry and molecular quantum dynamics. This theoretical framework allows for rationalizing the generation of molecular rovibrational coherence from thermally hot atoms [L. Rybak \textit{et al.}, Phys. Rev. Lett. {\bf 107}, 273001 (2011)]. Random phase thermal wave functions are employed to model the thermal ensemble of hot colliding atoms. Comparing two different choices of basis func…
Four problematic circumstances are considered, involving models which describe dynamical wavefunction collapse toward energy eigenstates, for which it is shown that wavefunction collapse of macroscopic objects does not work properly. In one case, a common particle position measuring situation, the apparatus evolves to a superposition of macroscopically distinguishable states (does not collapse to one of them as it should) because each such particle/apparatus/environment state has precisely the same energy spectrum. Second, assuming an experiment takes place involving collapse to one of two pos…
Highly accurate closed-form approximations are given for the ground state and first excited state wavefunctions and energies for a nonrelativistic particle in a one-dimensional double square well potential with a square barrier in between (so that the potential is a sequence of five constant pieces that alternate in value from being above and below the ground state and first excited state energies), under the assumption that the barrier is sufficiently wide that the tunneling across it is very small.
A coherent mechanism of robust population inversion in atomic and molecular systems by a chirped field is presented. It is demonstrated that a field of sufficiently high chirp rate imposes a certain relative phase between a ground and excited state wavefunction of a two-level system. The value of the relative phase angle is thus restricted to be negative and close to 0 or $-π$ for positive and negative chirp, respectively. This explains the unidirectionality of the population transfer from the ground to the excited state. In a molecular system composed of a ground and excited potential energy …
We show that excited-state quantum phase transitions (ESQPTs) in a system in which the parity symmetry is broken can be used to engineer an energy-cat state -- a Schrödinger cat state involving a quantum superposition of both different positions and energies. By means of a generalization of the Rabi model, we show that adding a parity-breaking term annihilates the ground-state quantum phase transition between normal and superradiant phases, and induces the formation of three excited-state phases, all of them identified by means of an observable with two eigenvalues. In one of these phases, lev…
Point-group symmetry analysis of many-electron wavefunctions on a quantum computer
JSR Corporation（杰士创株式会社）；Keio University（庆应义塾大学）；Deloitte Tohmatsu LLC（德勤都马茨有限责任公司）；TCG Centres for Research and Education in Science and Technology（TCG科学与技术研究与教育中心）；Mitsubishi Chemical Corporation（三菱化学株式会社）；IBM Quantum, IBM Research–Tokyo（IBM量子，IBM研究-东京）
By going beyond Hubbard Hamiltonian we reflected correlation effects accurately in the wavefunctions of H2. Using ab initio e-e interaction parameters resulted maximally entangled ground and third excited states. We assigned this maximally entangled character to the nonmagnetic (S=0) property of these states and also the minimally entangled character of the first excited states to its magnetic property. By switching on a magnetic field an entangled state with Sz = 0 can be extracted from a minimally entangled degenerate magnetic state. We suggest that presence of a moderate correlated system a…
Cuprous oxide (Cu${}_2$O) has recently been proposed as a promising solid-state host for excitonic Rydberg states with large principal quantum numbers ($n$), whose exaggerated wavefunction sizes ($\propto n^2)$ facilitate gigantic dipole-dipole ($\propto n^4$) and van der Waals ($\propto n^{11}$) interactions, making them an ideal basis for solid-state quantum technology. Synthetic, thin-film Cu${}_2$O samples are of particular interest because they can be made defect-free via carefully controlled fabrication and are, in principle, suitable for the observation of extreme single-photon nonlinea…
We extend the notion of quantum blob studied in previous work to excited states of the generalized harmonic oscillator in n dimensions. This extension is made possible by Fermi's observation in 1930 that the state of a quantum system may be defined in two different (but equivalent) ways, namely by its wavefunction Ψ or by a certain function g_{F} on phase space canonically associated with Ψ. We study Fermi's function when Ψ is a Gaussian (generalized coherent state). A striking result is that we can use the Ekeland--Hofer symplectic capacities to characterize the Fermi functions of the excited…
