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arXiv:1107.1105 · The Journal of Chemical Physics

Quantum entanglement between electronic and vibrational degrees of freedom in molecules

L. K. McKemmish, Ross H. McKenzie, Noel S. Hush, Jeffrey R. Reimers

Published Dec 28, 2011• 70 citations
arXivHTMLPDF

Abstract

We consider the quantum entanglement of the electronic and vibrational degrees of freedom in molecules with tendencies towards double welled potentials. In these bipartite systems, the von Neumann entropy of the reduced density matrix is used to quantify the electron-vibration entanglement for the lowest two vibronic wavefunctions obtained from a model Hamiltonian based on coupled harmonic diabatic potential-energy surfaces. Significant entanglement is found only in the region in which the ground vibronic state contains a density profile that is bimodal (i.e., contains two separate local maxima). However, in this region two distinct types of density and entanglement profiles are found: one type arises purely from the degeneracy of energy levels in the two potential wells and is destroyed by slight asymmetry, while the other arises through strong interactions between the diabatic levels of each well and is relatively insensitive to asymmetry. These two distinct types are termed fragile degeneracy-induced entanglement and persistent entanglement, respectively. Six classic molecular systems describable by two diabatic states are considered: ammonia, benzene, BNB, pyridine excited triplet states, the Creutz-Taube ion, and the radical cation of the "special pair" of chlorophylls involved in photosynthesis. These chemically diverse systems are all treated using the same general formalism and the nature of the entanglement that they embody is elucidated.

DOI
10.1063/1.3671386

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We consider the quantum entanglement of the electronic and vibrational degrees of freedom in molecules with tendencies towards double welled potentials. In these bipartite systems, the von Neumann entropy of the reduced density matrix is used to quantify the electron-vibration entanglement for the lowest two vibronic wavefunctions obtained from a model Hamiltonian based on coupled harmonic diabatic potential-energy surfaces. Significant entanglement is found only in the region in which the ground vibronic state contains a density profile that is bimodal (i.e., contains two separate local maxima). However, in this region two distinct types of density and entanglement profiles are found: one type arises purely from the degeneracy of energy levels in the two potential wells and is destroyed by slight asymmetry, while the other arises through strong interactions between the diabatic levels of each well and is relatively insensitive to asymmetry. These two distinct types are termed fragile degeneracy-induced entanglement and persistent entanglement, respectively. Six classic molecular systems describable by two diabatic states are considered: ammonia, benzene, BNB, pyridine excited triplet states, the Creutz-Taube ion, and the radical cation of the "special pair" of chlorophylls involved in photosynthesis. These chemically diverse systems are all treated using the same general formalism and the nature of the entanglement that they embody is elucidated.
We investigate the entanglement between electronic and vibrational degrees of freedom produced by a vibronic coupling in a molecular system described in the Born-Oppenheimer approximation. Entanglement in a pure state of the Hilbert space H=Hel⨂Hvib\mathcal{H}={\mathcal{H}}_{\mathrm{el}}⨂{\mathcal{H}}_{\mathrm{vib}}H=Hel​⨂Hvib​ is quantified using the von Neumann entropy of the reduced density matrix and the reduced linear entropy. Expressions for these entanglement measures are derived for the $2\ifmmode\times\else\texttimes\fi{}{N}_{v}$ and $3\ifmmode\times\else\texttimes\fi{}{N}_{v}$ cases of the bipartite entanglement, where 2 and 3 are the dimensions of the electronic Hilbert space H\mathcal{H}Hel{}_{\mathrm{el}}el​, and Nv{N}_{v}Nv​ is the dimension of H\mathcal{H}Hvib{}_{\mathrm{vib}}vib​. We study the entanglement dynamics for two electronic states coupled by a laser pulse (a $2\ifmmode\times\else\texttimes\fi{}{N}_{v}$ case), taking as an example a coupling between the ${a}^{3}{{\ensuremath{\Sigma}}_{u}}^{+}(6s,6s)$ and 1g(6s,6p3/2){1}_{g}(6s,6{p}_{3/2})1g​(6s,6p3/2​) states of the Cs2{}_{2}2​ molecule. The reduced linear entropy expression obtained for the $3\ifmmode\times\else\texttimes\fi{}{N}_{v}$ case is used to follow the entanglement evolution in a scheme proposed for the control of the vibronic dynamics in a Cs2{}_{2}2​ cold molecule, implying the ${a}^{3}{{\ensuremath{\Sigma}}_{u}}^{+}(6s,6s)$, ${0}_{g}{}^{\ensuremath{-}}(6s,6{p}_{3/2})$, and ${0}_{g}{}^{\ensuremath{-}}(6s,5d)$ electronic states, which are coupled by a nonadiabatic radial coupling and a sequence of chirped laser pulses.
We characterize both entanglement and quantum coherence in a molecular system by connecting the linear entropy of electronic-nuclear entanglement with Wigner-Yanase skew information measuring vibronic coherence and local quantum uncertainty on electronic energy. Linear entropy of entanglement and quantifiers of quantum coherence are derived for a molecular system described in a bipartite Hilbert space H=Hel⨂Hvib\mathcal{H}={\mathcal{H}}_{el}⨂{\mathcal{H}}_{vib}H=Hel​⨂Hvib​ of finite dimension ${N}_{el}\ifmmode\times\else\texttimes\fi{}{N}_{v}$, and relations between them are established. For the specific case of the electronic-vibrational entanglement, we find the linear entropy of entanglement as having a more complex informational content than the von Neumann entropy. By keeping the information carried by the vibronic coherences in a molecule, linear entropy seizes vibrational motion in the electronic potentials as entanglement dynamics. We analyze entanglement oscillations in an isolated molecule, and show examples for the control of entanglement dynamics in a molecule through the creation of coherent vibrational wave packets in several electronic potentials by using chirped laser pulses.
ABSTRACT: In the present work, we have computed the entanglement between the electronic and nuclear motions in two molecular model systems: the one-dimensional hydrogen molecular ion (H2+) and the Shin-Metiu model, considering the molecules as a bipartite systems: electron and nuclear motion. For that purpose, we have computed the Born-Oppenheimer and non-Born-Oppenheimer (Born-Huang) wave function in terms of the Fourier Grid Hamiltonian basis that expands both the electronic and nuclear wave functions. Also, according to the Schmidt decomposition theorem for bipartite systems, widely used in quantum-information theory, there is a much shorter but equivalent expansion in terms of the Schmidt bases for the electronic and nuclear sub-spaces. In these models of distinguishable coupled particles we have shown that the entanglements contents do not increase monotonically with the excitation energy. In the hydrogen molecular ion and in the ShinMetiu model, the entanglements contents for each Born-Oppenheimer electro-nuclear state is quantified through the von-Neumann and linear entropies and we have shown that entanglement serves as a witness of distinguishability of nuclear states related to different Born-Oppenheimer molecular energy curves or electronic excitation modes.
In this thesis, we will analyze quantum entanglement phenomena in systems composed of quantum molecules, considering two different models. In the first, N molecules, each with a single excess electron, interact via Coulomb coupling. This interaction is restricted to the first neighbors. In the second system, electrons from distinct molecules interact with each other through the electron-phonon coupling. Considering the N-molecule system, we broadened our studies started in the master’s degree to verify the characteristics of the energy spectrum and eigenstates for the molecule system. We focus on the scalability of the system and its effect on entanglement, showing that some specific eigenstates are systematically associated with the maximally entangled GHZ states, regardless of the number of molecules. In the second part of the work, we explore the entanglement of both the electronic subsystem and the phonon subsystem, defining a new base composed of Bell’s electronic states associated with the excitation states in vibrational modes, which allows rewriting the Hamiltonian to the composite system. From this point of view, it is possible to determine a set of 4 ⊗ 4 matrix subspaces that elucidated the study of the entanglement behavior in both subsystems, allowing the determination of distinct sets of parameters effective in generating highly entangled states in the electronic subsystem and now in the phononic subsystem.
We compute the entanglement between the electronic and vibrational motions in the simplest molecular system, the hydrogen molecular ion, considering the molecule as a bipartite system, electron and vibrational motion. For that purpose we compute an accurate total non-Born-Oppenheimer wave function in terms of a huge expansion using nonorthogonal B-spline basis sets that expand separately the electronic and nuclear wave functions. According to the Schmidt decomposition theorem for bipartite systems, widely used in quantum-information theory, it is possible to find a much shorter but equivalent expansion in terms of the natural orbitals or Schmidt bases for the electronic and nuclear half spaces. Here we extend the Schmidt decomposition theorem to the case in which nonorthogonal bases are used to span the partitioned Hilbert spaces. This extension is first illustrated with two simple coupled systems, the former without an exact solution and the latter exactly solvable. In these model systems of distinguishable coupled particles it is shown that the entanglement content does not increase monotonically with the excitation energy, but only within the manifold of states that belong to an existing excitation mode, if any. In the hydrogen molecular ion the entanglement content for each non-Born-Oppenheimer vibronic state is quantified through the von Neumann and linear entropies and we show that entanglement serves as a witness to distinguish vibronic states related to different Born-Oppenheimer molecular energy curves or electronic excitation modes.
This article investigates entanglement of the motional states of massive coupled oscillators. The specific realization of an idealized diatomic molecule in one-dimension is considered, but the techniques developed apply to any massive particles with two degrees of freedom and a quadratic Hamiltonian. We present two methods, one analytic and one approximate, to calculate the interatomic entanglement for Gaussian and non-Gaussian pure states as measured by the purity of the reduced density matrix. The cases of free and trapped molecules and hetero- and homonuclear molecules are treated. In general, when the trap frequency and the molecular frequency are very different, and when the atomic masses are equal, the atoms are highly-entangled for molecular coherent states and number states. Surprisingly, while the interatomic entanglement can be quite large even for molecular coherent states, the covariance of atomic position and momentum observables can be entirely explained by a classical model with appropriately chosen statistical uncertainty.