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arXiv:1811.08220 · Physical Review A

Non-Markovian dynamics of the electronic subsystem in a laser-driven molecule: Characterization and connections with electronic-vibrational entanglement and electronic coherence

Mihaela Vatasescu

Published Nov 19, 2018• 3 citations
arXivHTMLPDF

Abstract

Non-Markovian quantum evolution of the electronic subsystem in a laser-driven molecule is characterized through the appearance of negative decoherence rates in the canonical form of the electronic master equation. For a driven molecular system described in a bipartite Hilbert space $\mathcal{H}={\mathcal{H}}_{el}⨂{\mathcal{H}}_{\mathrm{vib}}$ of dimension $2\ifmmode\times\else\texttimes\fi{}{N}_{v}$, we derive the canonical form of the electronic master equation, deducing the canonical measures of non-Markovianity and the Bloch volume of accessible states. We find that one of the decoherence rates is always negative, accounting for the inherent non-Markovian character of the electronic evolution in the vibrational environment. Enhanced non-Markovian behavior, characterized by two negative decoherence rates, appears if there is a coupling between the electronic states $g,\phantom{\rule{0.16em}{0ex}}e$, such that the evolution of the electronic populations obeys $d({P}_{g}{P}_{e})/dt>0$. Non-Markovianity of the electronic evolution is analyzed in relation to temporal behaviors of the electronic-vibrational entanglement and electronic coherence, showing that enhanced non-Markovian behavior accompanies entanglement increase. Taking as an example the coupling of two electronic states by a laser pulse in the ${\mathrm{Cs}}_{2}$ molecule, we analyze non-Markovian dynamics under laser pulses of various strengths, finding that the weaker pulse stimulates the bigger amount of non-Markovianity. Our results show that increase of the electronic-vibrational entanglement over a time interval is correlated to the growth of the total amount of non-Markovianity calculated over the same interval using canonical measures and connected with the increase of the Bloch volume. After the pulse, non-Markovian behavior is correlated to electronic coherence, such that vibrational motion in the electronic potentials which diminishes the nuclear overlap, implicitly increasing the linear entropy of entanglement, brings a memory character to dynamics.

DOI
10.1103/physreva.98.053426

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Non-Markovian quantum evolution of the electronic subsystem in a laser-driven molecule is characterized through the appearance of negative decoherence rates in the canonical form of the electronic master equation. For a driven molecular system described in a bipartite Hilbert space H=Hel⨂Hvib\mathcal{H}={\mathcal{H}}_{el}⨂{\mathcal{H}}_{\mathrm{vib}}H=Hel​⨂Hvib​ of dimension 2\ifmmode×\else\texttimes\fiNv2\ifmmode\times\else\texttimes\fi{}{N}_{v}2\ifmmode×\else\texttimes\fiNv​, we derive the canonical form of the electronic master equation, deducing the canonical measures of non-Markovianity and the Bloch volume of accessible states. We find that one of the decoherence rates is always negative, accounting for the inherent non-Markovian character of the electronic evolution in the vibrational environment. Enhanced non-Markovian behavior, characterized by two negative decoherence rates, appears if there is a coupling between the electronic states g,eg,\phantom{\rule{0.16em}{0ex}}eg,e, such that the evolution of the electronic populations obeys d(PgPe)/dt>0d({P}_{g}{P}_{e})/dt>0d(Pg​Pe​)/dt>0. Non-Markovianity of the electronic evolution is analyzed in relation to temporal behaviors of the electronic-vibrational entanglement and electronic coherence, showing that enhanced non-Markovian behavior accompanies entanglement increase. Taking as an example the coupling of two electronic states by a laser pulse in the Cs2{\mathrm{Cs}}_{2}Cs2​ molecule, we analyze non-Markovian dynamics under laser pulses of various strengths, finding that the weaker pulse stimulates the bigger amount of non-Markovianity. Our results show that increase of the electronic-vibrational entanglement over a time interval is correlated to the growth of the total amount of non-Markovianity calculated over the same interval using canonical measures and connected with the increase of the Bloch volume. After the pulse, non-Markovian behavior is correlated to electronic coherence, such that vibrational motion in the electronic potentials which diminishes the nuclear overlap, implicitly increasing the linear entropy of entanglement, brings a memory character to dynamics.
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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.
Master equations govern the time evolution of a quantum system interacting with an environment, and may be written in a variety of forms. Time-independent or memoryless master equations, in particular, can be cast in the well-known Lindblad form. Any time-local master equation, Markovian or non-Markovian, may in fact also be written in a Lindblad-like form. A diagonalization procedure results in a unique, and in this sense canonical, representation of the equation, which may be used to fully characterize the non-Markovianity of the time evolution. Recently, several different measures of non-Markovianity have been presented which reflect, to varying degrees, the appearance of negative decoherence rates in the Lindblad-like form of the master equation. We therefore propose using the negative decoherence rates themselves, as they appear in the canonical form of the master equation, to completely characterize non-Markovianity. The advantages of this are especially apparent when more than one decoherence channel is present. We show that a measure proposed by Rivas et al. [Phys. Rev. Lett. 105, 050403 (2010)] is a surprisingly simple function of the canonical decoherence rates, and give an example of a master equation that is non-Markovian for all times t>0t>0t>0, but to which nearly all proposed measures are blind. We also give necessary and sufficient conditions for trace distance and volume measures to witness non-Markovianity, in terms of the Bloch damping matrix.
We determine the total state dynamics of a dephasing open quantum system using the standard environment of harmonic oscillators. Of particular interest are random unitary approaches to the same reduced dynamics and system-environment correlations in the full model. Concentrating on a model with an at times negative dephasing rate, the issue of non-Markovianity will also be addressed. Crucially, given the quantum environment, the appearance of non-Markovian dynamics turns out to be accompanied by a loss of system-environment correlations. Depending on the initial purity of the qubit state, these system-environment correlations may be purely classical over the whole relevant time scale, or there may be intervals of genuine system-environment entanglement. In the latter case, we see no obvious relation between the build-up or decay of these quantum correlations and Non-Markovianity.
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We investigate signatures of non-Markovianity in the dynamics of a periodically driven qubit coupled to a dissipative bosonic environment. We propagate the dynamics of the reduced density matrix of the qubit by integrating the numerically exact hierarchical equations of motion. Non-Markovian features are quantified by comparing on an equal footing the predictions from diverse and complementary approaches to quantum dissipation. In particular, we analyze the distinguishability of quantum states, the decay of the volume accessible to the qubit on the Hilbert space, the negativity of the canonical rates in the generalized Lindblad equation, and the relaxation of the memory kernels in the Nakajima-Zwanzig generalized quantum master equation. We study the effects of controlled driving on the coherent dynamics of the system. We show that a suitable external field can offset the ergodic relaxation of time-correlation functions, increase distinguishability over time, and strengthen non-Markovian effects witnessed by the canonical dissipation channels. We furthermore observe the phenomenon of eternal non-Markovianity for sufficiently small system-bath coupling and we discuss how this can be enhanced by modulating the frequency of the external drive. This work provides a broad theoretical analysis of quantum dissipation in the framework of open quantum dynamics and quantum information.