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Quantum Electrodynamical time-dependent density functional theory

Camilla Pellegrini

Published Sep 21, 2017• 0 citations
OpenAlex

Abstract

The last two decades have witnessed increasing experimental interest in the study and control of many-electron systems strongly interacting with quantum electromagnetic fields. This includes notable experiments in the areas of cavity and circuit quantum electrodynamics, quantum computing via photon mediated atom entanglement, electromagnetically induced transparency, quantum plasmonics, quantum simulators and chemistry. The description of realistic coupled matter-photon systems requires combining electronic structure methods from material science with quantum-optical methods. In this work, we propose a formally exact and numerically feasible approach, termed quantum electrodynamical time-dependent density functional theory (QED-TDDFT), that generalizes successful TDDFT for electronic structure calculations, to the electron-photon coupling. We develop a general framework for the description of coupled matter-photon systems in all possible realizations of interest, ranging from the fully relativistic case, to well-known quantum-optical model (e.g., the Rabi model). Of particular interest for condensed-matter applications is the density functionalisation of non-relativistic QED. The underlying theory in fact corresponds to standard non-relativistic quantum mechanics for the electrons, but with additional terms, which correct for relativity and electron-photon interactions. However, any application of density-functional theory requires approximations to the exchange-correlation (xc) functional. In this work we construct such an approximation for the description of electron-photon interaction effects in an optical cavity (the theory of reference is QED-TDDFT for many-electron systems coupled to cavity photons). The derived electron-photon optimized effective potential (OEP) reduces in the static limit to the Lamb shift of the ground state. The OEP is then tested on the Rabi model from weak to strong coupling regimes. The results are promising and open a path for describing complex strongly coupled matter-photon systems. Further, we consider the inclusion of relativistic spin-spin effects into the xc functional of standard spin density functional theory. In this way we provide quantum corrections that are essential for the description of magnetic inhomogeneities at the nanoscale. Such an approach improves over the current (classical) micromagnetic treatment of domain walls and skyrmions for spintronic applications.

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The last two decades have witnessed increasing experimental interest in the study and control of many-electron systems strongly interacting with quantum electromagnetic fields. This includes notable experiments in the areas of cavity and circuit quantum electrodynamics, quantum computing via photon mediated atom entanglement, electromagnetically induced transparency, quantum plasmonics, quantum simulators and chemistry. The description of realistic coupled matter-photon systems requires combining electronic structure methods from material science with quantum-optical methods. In this work, we propose a formally exact and numerically feasible approach, termed quantum electrodynamical time-dependent density functional theory (QED-TDDFT), that generalizes successful TDDFT for electronic structure calculations, to the electron-photon coupling. We develop a general framework for the description of coupled matter-photon systems in all possible realizations of interest, ranging from the fully relativistic case, to well-known quantum-optical model (e.g., the Rabi model). Of particular interest for condensed-matter applications is the density functionalisation of non-relativistic QED. The underlying theory in fact corresponds to standard non-relativistic quantum mechanics for the electrons, but with additional terms, which correct for relativity and electron-photon interactions. However, any application of density-functional theory requires approximations to the exchange-correlation (xc) functional. In this work we construct such an approximation for the description of electron-photon interaction effects in an optical cavity (the theory of reference is QED-TDDFT for many-electron systems coupled to cavity photons). The derived electron-photon optimized effective potential (OEP) reduces in the static limit to the Lamb shift of the ground state. The OEP is then tested on the Rabi model from weak to strong coupling regimes. The results are promising and open a path for describing complex strongly coupled matter-photon systems. Further, we consider the inclusion of relativistic spin-spin effects into the xc functional of standard spin density functional theory. In this way we provide quantum corrections that are essential for the description of magnetic inhomogeneities at the nanoscale. Such an approach improves over the current (classical) micromagnetic treatment of domain walls and skyrmions for spintronic applications.
Providing sufficient accuracy at low-computational cost, not surprisingly, density-functional theory ( DFT ) is a standard tool in theoretical material science. Similarly, quantum-electrodynamical density-functional theory ( QEDFT ) provides a promising route to describe experiments at the interface of quantum optics and quantum chemistry. Formally, in the Kohn-Sham ( KS ) formulation of DFT and QEDFT the exact many-particle Schrödinger equation is replaced by a set of coupled non-linear one-particle differential equations. The electron-electron, the electron-ion and the electron-photon interactions of the interacting system are mimicked by their corresponding effective KS potential with an, in principle unknown exchange-correlation ( xc ) term. In practice, DFT and QEDFT require approximations for this xc potential. The quality of which fully determines how much the DFT and QEDFT observables deviate from the exact ones. Understanding the shortcomings and improving the quality of approximate functionals makes the study of the exact functional of model systems indispensable. Here, we employ exact diagonalization for the Hamiltonian of different types of real-space lattice models in one spatial dimension to access the ground-state wave function, and thus to explicitly construct the exact functionals of DFT and QEDFT . To study the functional behavior of purely electronic systems, we consider two singlet-state electrons moving in an external potential with two connected atomic wells of variable depth and distance. To study coupled electron-photon systems, we consider the Rabi Hamiltonian with variable electron-photon coupling strength. By varying the model parameters, we systematically construct the functionals for systems from weak to strong coupling between the building blocks of the global system. Using the concept of the effective density-to- potential map, we discuss the intrasystem steepening which is an exact condition on the xc functional that captures the static correlation present in the system and carve out how it relates to the well-known intersystem derivative discontinuity. We further construct arbitrary observables as functionals of the internal variables which are directly affected by such features of the effective density-to-potential map. By constructing the reduced dipole map in the four-particle case of coupled electron-photon system, we show that the density-to-potential map helps to identify and understand recently discovered physical effects in the field of strongly coupled electron-photon systems. This work provides a contribution to the development of approximate function- als required in practical density-functional calculations of arbitrary experimentally accessible observables. Both the intrasystem steepening and the intersystem derivative discontinuity play a crucial role for systems with highly-localized electrons. Including both features in approximate functionals will improve the accu- racy of DFT evaluation of observables for such systems. Those results provide novel insight into the properties of the exact xc potentials in QEDFT . This work opens a new route to construct new functionals using coarse-grained or embed- ding approaches within the general and exact frameworks of DFT and QEDFT.
We present results of a photon-free exchange-correlation functional within the local density approximation (pxcLDA) for quantum electrodynamics density functional theory (QEDFT) that efficiently describes the electron density of many-electron systems across weak to strong light-matter coupling. Building on previous work [I-Te. Lu et al., Phys. Rev. A 109, 052823 (2024)] that captured electron-photon correlations via an exchange-correlation functional derived from the nonrelativistic Pauli-Fierz Hamiltonian and tested on one-electron systems, we use a simple procedure to compute a renormalization factor describing electron-photon correlations and inhomogeneity in the weak-coupling regime by comparing it with quantum electrodynamics coupled-cluster, and previous QEDFT optimized effective potential methods. Across various atoms and molecules, pxcLDA reproduces cavity-modified densities in close agreement with these references. The renormalization factor approaches unity as the system size or collective coupling increases, reflecting an electron-photon exchange-dominated behavior and improved accuracy for larger systems. This approach now offers a practical route to applying QEDFT functionals based on electron density to realistic electron systems.
In this work, we provide an overview of how well-established concepts in the fields of quantum chemistry and material sciences have to be adapted when the quantum nature of light becomes important in correlated matter-photon problems. We analyze model systems in optical cavities, where the matter-photon interaction is considered from the weak- to the strong-coupling limit and for individual photon modes as well as for the multimode case. We identify fundamental changes in Born-Oppenheimer surfaces, spectroscopic quantities, conical intersections, and efficiency for quantum control. We conclude by applying our recently developed quantum-electrodynamical density-functional theory to spontaneous emission and show how a straightforward approximation accurately describes the correlated electron-photon dynamics. This work paves the way to describe matter-photon interactions from first principles and addresses the emergence of new states of matter in chemistry and material science.
First-principles electronic structure theory explains properties of atoms, molecules and solids from underlying physical principles without input from empirical parameters. Time-dependent density functional theory (TDDFT) has emerged as arguably the most widely used first-principles method for describing the time-dependent quantum mechanics of many-electron systems. In this thesis, we will show how the fundamental principles of TDDFT can be extended and applied in two novel directions: The theory of open quantum systems (OQS) and quantum computation (QC). In the first part of this thesis, we prove theorems that establish the foundations of TDDFT for open quantum systems (OQS-TDDFT). OQS-TDDFT allows for a first principles description of non-equilibrium systems, in which the electronic degrees of freedom undergo relaxation and decoherence due to coupling with a thermal environment, such as a vibrational or photon bath. We then discuss properties of functionals in OQS-TDDFT and investigate how these differ from functionals in conventional TDDFT using an exactly solvable model system. Next, we formulate OQS-TDDFT in the linear-response regime, which gives access to environmentally broadened excitation spectra. Lastly, we present a hybrid approach in which TDDFT can be used to construct master equations from first-principles for describing energy transfer in condensed phase systems. In the second part of this thesis, we prove that the theorems of TDDFT can be extended to a class of qubit Hamiltonians that are universal for quantum computation. TDDFT applied to universal Hamiltonians implies that single-qubit expectation values can be used as the basic variables in quantum computation and information theory, rather than wavefunctions. This offers the possibility of simplifying computations by using the principles of TDDFT similar to how it is applied in electronic structure theory. Lastly, we discuss a related result; the computational complexity of TDDFT.
This thesis is devoted to the formulation and implications of the time-dependent density functional theory (TDDFT). The work is divided into two main parts. In the first part we develop rigorous theorems for the density-potential mapping in quantum many-body systems on a lattice. We prove the uniqueness of the TDDFT map and demonstrate that a given density is v-representable if the initial many-body state and the density satisfy certain well defined conditions. In particular, we show that for a system evolving from its ground state any density with a continuous second time derivative is v-representable. Then the lattice TDDFT formulation is extended to cover system of interacting lattice electrons strongly coupled to cavity photons.We prove that under some mathematical conditions the electron-photon wave function is a unique functional of the electronic density and the expectation value of the photonic coordinate. Then we further generalize the ground state v representability theorem to include the ground state of a general lattice electron-photon Hamiltonian.
Time-dependent density functional theory (TDDFT) provides a successful approach to calculate excitation energies of atomic and molecular systems. In part I of this work we present a double-pole approximation (DPA) to the response equations of TDDFT. The double-pole approximation provides an exact description of systems with two strongly coupled excitations which are isolated from the rest of the spectrum. In contrast to the traditional single- pole approximation of TDDFT the DPA also yields corrections to the Kohn-Sham oscillator strengths. Several critical pole separations can be identified, e.g. we find that the pole coupling can cause transitions to vanish entirely from the optical spectrum. We also demonstrate how to invert the double-pole solution which allows us to predict matrix elements of the exchange- correlation kernel fxc from experimental input. This can serve as benchmark for the construction of future approximations for the kernel fxc. Reduced density matrix functional theory (RDMFT) has emerged recently as promising candidate to treat strongly correlated electronic many-body systems beyond traditional density functional theory (DFT). The research within RDMFT was so far focussed on the static theory. In this work we attempt some first steps towards a time-dependent generalization of RDMFT. In part II we derive equations of motion for natural orbitals and occupation numbers. Using the equation of motion for the occupation numbers we show that an adiabatic extension of presently known ground-state functionals of static RDMFT always leads to occupation numbers which are constant in time. From the stationary conditions of the equations of motion for the N-body correlations (correlated parts of the N-body matrices) we derive a new class of ground-state functionals which can be used in static RDMFT. Applications are presented for a one-dimensional model system where the time-dependent many-body Schrödinger equation can be propagated numerically. We use optimal control theory to find optimized laser pulses for transitions in a model for atomic Helium. From the numerically exact correlated wavefunction we extract the exact time evolution of natural orbitals and occupation numbers for (i) laser-driven Helium and (ii) electron-ion scattering. Part III of this work considers time-dependent quantum transport within TDDFT. We present an algorithm for the calculation of extended eigenstates of single- particle Hamiltonians which is especially tailored to a finite-difference discretization of the Schrödinger equation. We consider the propagation of finite mesoscopic systems and demonstrate the limitations of such an approach. To overcome the shortcomings of a description of quantum transport in terms of finite systems we develop a time-propagation scheme for extended states which utilizes a mixed basis representation. Our discretization scheme allows to treat central device and lead regions on the same footing thus preventing artificial reflections at grid boundaries.