Quantum optimal control theory for solvated systems

Rosa, Marta; Gil, Gabriel; Corni, Stefano; Cammi, Roberto

doi:10.1063/1.5125184

Cited by 11 publications

(10 citation statements)

References 47 publications

(121 reference statements)

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“…A notable example is represented by the well established Rabitz algorithm [10], which shows excellent convergence properties both in vacuum and in the presence of a solvent [40]. Despite its success, this algorithm is intrinsically unsuitable to be used coupled with a quantum simulation algorithm, as it requires the knowledge of the state of the system at each instant of its evolution.…”

Section: A Optimization Of the J Functionalmentioning

confidence: 99%

“…The first 10 electronic excited states were computed with GAMESS [51] at the CIS level of theory using a 6-31G * * basis set. The suitability of the number of excited states considered to evaluate the optimal dynamics involving a sufficiently large set of electronic states is assumed on the basis of a previous related work [40]. It may be worth noticing that, when OC is applied to an actual experimental situation , a more accurate description of the system is needed; the CIS method is usually affected by excitation energies overestimation [52], nevertheless an accurate description of the molecule electronic structure goes beyond the purpose of the present study.…”

Section: Computational Detailsmentioning

confidence: 99%

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Quantum optimal control with quantum computers: an hybrid algorithm featuring machine learning optimization

Castaldo,

Rosa,

Corni

2020

Preprint

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We develop an hybrid quantum-classical algorithm to solve an optimal population transfer problem for a molecule subject to a laser pulse. The evolution of the molecular wavefunction under the laser pulse is simulated on a quantum computer, while the optimal pulse is iteratively shaped via a machine learning (evolutionary) algorithm. A method to encode on the quantum computer the n-electrons wavefunction is discussed, the circuits accomplishing its quantum simulation are derived and the scalability in terms of number of operations is discussed. Performance on Noisy Intermediate-Scale Quantum devices (IBM Q X2) is provided to assess the current technological gap. Furthermore the hybrid algorithm is tested on a quantum emulator to compare performance of the evolutionary algorithm with standard ones. Our results show that such algorithms are able to outperform the optimization with a downhill simplex method and provide performance comparable to more advanced (but quantum-computer unfriendly) algorithms such as Rabitz's.

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Section: A Optimization Of the J Functionalmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Quantum optimal control with quantum computers: an hybrid algorithm featuring machine learning optimization

Castaldo,

Rosa,

Corni

2020

Preprint

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“…Here, we report the results of the application of TDDFT and GW/BSE postprocessing, i.e., populations, induced density, ΔPDOS, and TCM, on the HBDI molecule, which is the chromophore of the GFP protein, − the DNQDI fluorophore, which has been used to study the interplay between electronic and vibrational quantum coherence, , the LiCN molecule, which has been chosen as a computational model for dipole switching, as reported in the literature, ,,,, and a small metal cluster Ag 22 , which is the prototype of systems with collective optical responses . The ground-state equilibrium structures of these systems are reported in Figure .…”

Section: Introductionmentioning

confidence: 99%

Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms

Illobre

Marsili

Corni

et al. 2021

J. Chem. Theory Comput.

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In this work, a theoretical and computational set of tools to study and analyze time-resolved electron dynamics in molecules, under the influence of one or more external pulses, is presented. By coupling electronic-structure methods with the resolution of the time-dependent Schrodinger equation, we developed and implemented the time-resolved induced density of the electronic wavepacket, the time-resolved formulation of the differential projection density of states (ΔPDOS), and of transition contribution map (TCM) to look at the single-electron orbital occupation and localization change in time. Moreover, to further quantify the possible charge transfer, we also defined the energy-integrated ΔPDOS and the fragmentprojected TCM. We have used time-dependent density-functional theory (TDDFT), as implemented in ADF software, and the Bethe−Salpeter equation, as provided by MolGW package, for the description of the electronic excited states. This suite of postprocessing tools also provides the time evolution of the electronic states of the system of interest. To illustrate the usefulness of these postprocessing tools, excited-state populations have been computed for HBDI (the chromophore of GFP) and DNQDI molecules interacting with a sequence of two pulses. Time-resolved descriptors have been applied to study the time-resolved electron dynamics of HBDI, DNQDI, LiCN (being a model system for dipole switching upon highest occupied molecular orbital−lowest unoccupied molecular orbital (HOMO−LUMO) electronic excitation), and Ag 22 . The computational analysis tools presented in this article can be employed to help the interpretation of fast and ultrafast spectroscopies on molecular, supramolecular, and composite systems.

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“…[24][25][26] Beyond the environment complexity available, this theoretical framework has been developed in many directions giving the possibility to describe the solute at different levels of theory, [27][28][29] picturing the overall process with the use of the open quantum system formalism 30 and also accounting for the presence of nanometallic structures 31 and optimal control procedures. 32 Finally, we also mention a recent development which exploits the emerging tool of machine learning to improve the estimates of solvation free-energy obtained from PCM. 33 In this contribution we leverage the standard formulation of the IEF-PCM to include solvation effects in the flagship algorithm of quantum simulation for Noisy Intermediate Scale Quantum (NISQ) devices: the Variational Quantum Eigensolver (VQE).…”

Section: Introductionmentioning

confidence: 99%

Quantum simulation of molecules in solution

Castaldo¹,

Jahangiri²,

Delgado³

et al. 2021

Preprint

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Quantum chemical calculations on quantum computers have been focused mostly on simulating molecules in gas-phase. Molecules in liquid solution are however most relevant for Chemistry. Continuum solvation models represent a good compromise between computational affordability and accuracy in describing solvation effects within a quantum chemical description of solute molecules. Here we report on the extension of the Variational Quantum Eigensolver to solvated systems, using the Polarizable Continuum Model. We show that accounting for solvation effects does not impact the algorithmic efficiency. Numerical results of noiseless simulations for molecular systems with up to twelve spin-orbitals (qubits) are presented. Furthermore, calculations performed on a simulated quantum hardware (IBM Q Mumbai), thus including noise, yield computed solvation free energies in fair agreement with the classical calculations without the inclusion of any error mitigation protocol.

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Quantum optimal control theory for solvated systems

Cited by 11 publications

References 47 publications

Quantum optimal control with quantum computers: an hybrid algorithm featuring machine learning optimization

Quantum optimal control with quantum computers: an hybrid algorithm featuring machine learning optimization

Time-Resolved Excited-State Analysis of Molecular Electron Dynamics by TDDFT and Bethe–Salpeter Equation Formalisms

Quantum simulation of molecules in solution

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