Quantum control of electronic fluxes during adiabatic attosecond charge migration in degenerate superposition states of benzene

Jia, Dongming; Manz, J.; Paulus, Beate; Pohl, Vincent; Tremblay, Jean Christophe; Yang, Yonggang

doi:10.1016/j.chemphys.2016.09.021

Cited by 58 publications

(65 citation statements)

References 87 publications

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“…A widespread quantity for the visual representation of electronic motions in molecular systems is the time‐dependent one‐electron density

ρ true(r, t true)

. It remains a useful tool to characterize the correlated electron dynamics from multideterminant wave functions of the form eq.…”

Section: Computational Procedures and Theorymentioning

confidence: 99%

“…Finally, initial conditions can be chosen such as to drive an interesting charge migration process that induces a periodic unidirectional circular current in the

H_{3}^{+}

plane. As was previously shown for other high‐symmetry ring‐shaped molecules, this can be achieved by a carefully chosen superposition of the ground state

1^{1} A_{1}^{'}

and the degenerate state

1^{1} E'

. In the basis of Full CI eigenstates used to study the N ‐electron dynamics, the field‐free evolution of the system is known analytically at all times.…”

Section: Numerical Examplesmentioning

confidence: 99%

“…The axis labels correspond to the molecular orientation as given in the quantum chemistry program. It was shown that it is possible to prepare such a wave packet by electronic excitation of the ground state using a circular polarized laser field . The time‐dependent electron density associated with this wave packet takes the form

\begin{matrix} left & ρ true(r, t true) = & \frac{1}{2} (ρ_{g} true(boldr true) + \frac{1}{2} ρ_{x} true(boldr true) + \frac{1}{2} ρ_{y} true(boldr true)) + \frac{1}{\sqrt{2}} ρ_{normalg x} true(boldr true) \cos (Δ E t) \\ left & + \frac{1}{\sqrt{2}} ρ_{normalg y} true(boldr true) \sin (Δ E t), \end{matrix}

with

Δ E = E_{e} - E_{g}

.…”

Section: Numerical Examplesmentioning

confidence: 99%

See 2 more Smart Citations

An open‐source framework for analyzing N‐electron dynamics. I. Multideterminantal wave functions

2017

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The aim of the present contribution is to provide a framework for analyzing and visualizing the correlated many-electron dynamics of molecular systems, where an explicitly time-dependent electronic wave packet is represented as a linear combination of N -electron wave functions. The central quantity of interest is the electronic flux density, which contains all information about the transient electronic density, the associated phase, and their temporal evolution. It is computed from the associated one-electron operator by reducing the multi-determinantal, many-electron wave packet using the Slater-Condon rules. Here, we introduce a general tool for post-processing multi-determinant configuration-interaction wave functions obtained at various levels of theory. It is tailored to extract directly the data from the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions. The procedure is implemented in the open-source Python program detCI@ORBKIT, which shares and builds upon the modular design of our recently published post-processing toolbox [J. Comput. Chem. 37 (2016) 1511]. The new procedure is applied to ultrafast charge migration processes in different molecular systems, demonstrating its broad applicability.Convergence of the N -electron dynamics with respect to the electronic structure theory level and basis set size is investigated. This provides an assessment of the robustness of qualitative and quantitative statements that can be made concerning dynamical features observed in charge migration simulations.

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“…A widespread quantity for the visual representation of electronic motions in molecular systems is the time‐dependent one‐electron density

ρ true(r, t true)

. It remains a useful tool to characterize the correlated electron dynamics from multideterminant wave functions of the form eq.…”

Section: Computational Procedures and Theorymentioning

confidence: 99%

“…Finally, initial conditions can be chosen such as to drive an interesting charge migration process that induces a periodic unidirectional circular current in the

H_{3}^{+}

plane. As was previously shown for other high‐symmetry ring‐shaped molecules, this can be achieved by a carefully chosen superposition of the ground state

1^{1} A_{1}^{'}

and the degenerate state

1^{1} E'

. In the basis of Full CI eigenstates used to study the N ‐electron dynamics, the field‐free evolution of the system is known analytically at all times.…”

Section: Numerical Examplesmentioning

confidence: 99%

\begin{matrix} left & ρ true(r, t true) = & \frac{1}{2} (ρ_{g} true(boldr true) + \frac{1}{2} ρ_{x} true(boldr true) + \frac{1}{2} ρ_{y} true(boldr true)) + \frac{1}{\sqrt{2}} ρ_{normalg x} true(boldr true) \cos (Δ E t) \\ left & + \frac{1}{\sqrt{2}} ρ_{normalg y} true(boldr true) \sin (Δ E t), \end{matrix}

with

Δ E = E_{e} - E_{g}

.…”

Section: Numerical Examplesmentioning

confidence: 99%

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An open‐source framework for analyzing N‐electron dynamics. I. Multideterminantal wave functions

2017

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show abstract

“…[1][2][3][4][5][6][7]), a process that it often followed by charge migration (as in Refs. [8][9][10][11][12][13][14][15][16][17][18]). Recently, we showed that one can employ a well-designed second laser pulse that restores the symmetry of the electronic structure after application of a first symmetry-breaking pulse [19][20][21].…”

Section: Introductionmentioning

confidence: 99%

From Symmetry Breaking via Charge Migration to Symmetry Restoration in Electronic Ground and Excited States: Quantum Control on the Attosecond Time Scale

2019

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This article starts with an introductory survey of previous work on breaking and restoring the electronic structure symmetry of atoms and molecules by means of two laser pulses. Accordingly, the first pulse breaks the symmetry of the system in its ground state with irreducible representation IRREP g by exciting it to a superposition of the ground state and an excited state with different IRREP e . The superposition state is non-stationary, representing charge migration with period T in the sub-to few femtosecond time domains. The second pulse stops charge migration and restores symmetry by de-exciting the superposition state back to the ground state. Here, we present a new strategy for symmetry restoration: The second laser pulse excites the superposition state to the excited state, which has the same symmetry as the ground state, but different IRREP e . The success depends on perfect time delay between the laser pulses, with precision of few attoseconds. The new strategy is demonstrated by quantum dynamics simulation for an oriented model system, benzene.

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“…Flux analyses have also been studied for nonadiabatic processes and charge migration dynamics in systems such as HCCl, benzene and LiH . We here present a flux analysis of full quantum mechanical dynamics of a nonadiabatic electron‐transfer process in the system of LiF ↔ Li + F ‐ to attain deeper insights about the break‐down of the Born–Oppenheimer approximation.…”

Section: Introductionmentioning

confidence: 99%

Electronic and nuclear flux analysis on nonadiabatic electron transfer reaction: A view from single‐configuration adiabatic born–huang representation

Matsuzaki

Takatsuka

2018

J Comput Chem

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A detailed flux analysis on nonadiabatically coupled electronic and nuclear dynamics in the intramolecular electron transfer of LiF is presented. Full quantum dynamics both of electrons and nuclei within two‐state model has uncovered interesting features of the individual fluxes (current of probability density) and correlation between them. In particular, a spatiotemporal oscillatory pattern of electronic flux has been revealed, which reflects the coherence coming from spatiotemporal differential overlap between nuclear wavepackets running on covalent and ionic potential curves. In this regard, a theoretical analogy between the nonadiabatic transitions and the Rabi oscillation is surveyed. We also present a flux–flux correlation between the nuclear and electronic motions, which quantifies the extent of deviation of the actual electronic and nuclear coupled dynamics from the Born–Oppenheimer adiabatic limit, which is composed only of a single product of the adiabatic electronic and nuclear wavefunctions. © 2018 Wiley Periodicals, Inc.

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Quantum control of electronic fluxes during adiabatic attosecond charge migration in degenerate superposition states of benzene

Cited by 58 publications

References 87 publications

An open‐source framework for analyzing N‐electron dynamics. I. Multideterminantal wave functions

An open‐source framework for analyzing N‐electron dynamics. I. Multideterminantal wave functions

From Symmetry Breaking via Charge Migration to Symmetry Restoration in Electronic Ground and Excited States: Quantum Control on the Attosecond Time Scale

Electronic and nuclear flux analysis on nonadiabatic electron transfer reaction: A view from single‐configuration adiabatic born–huang representation

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