Time-dependent coupled-cluster theory for ultrafast transient-absorption spectroscopy

Skeidsvoll, Andreas S.; Balbi, Alice; Koch, Henrik

doi:10.1103/physreva.102.023115

Cited by 24 publications

(64 citation statements)

References 39 publications

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“…Conservation laws in the framework of TDCC theory have been discussed at various levels of detail previously. 21,29,35,38,66,67 To this end, we recast the TDCC equations of motion in the Hamiltonian form…”

Section: Conservation Lawsmentioning

confidence: 99%

“…Yielding energies, structures, and properties with excellent accuracy for both ground-and excited states of weakly correlated systems, it has become one of the most trusted methods of molecular quantum chemistry. 15 Recent years have witnessed increasing interest in time-dependent CC (TDCC) theory [16][17][18][19][20] for numerical simulations of many-body quantum dynamics in nuclear, 21 and atomic and molecular [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] systems. In addition, TDCC theory plays a key role in recent work on finite-temperature CC theory for molecular 39,40 and extended 41 systems.…”

Section: Introductionmentioning

confidence: 99%

“…In many cases, the main goal is to compute absorption (or emission) spectra [24][25][26][27][28]37,38 by Fourier transformation of the induced dipole moment. This requires the calculation of the induced dipole moment for extended periods of time after the perturbing field or laser pulse has been turned off.…”

Section: Introductionmentioning

confidence: 99%

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Interpretation of Coupled-Cluster Many-Electron Dynamics in Terms of Stationary States

Pedersen,

Kristiansen,

Bodenstein

et al. 2020

Preprint

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We demonstrate theoretically and numerically that laser-driven many-electron dynamics, as described by bivariational time-dependent coupled-cluster theory, may be analyzed in terms of stationary-state populations. Projectors heuristically defined from linear response theory and equation-of-motion coupled-cluster theory are proposed for the calculation of stationary-state populations during interaction with laser pulses or other external forces, and conservation laws of the populations are discussed. Numerical tests of the proposed projectors, involving both linear and nonlinear optical processes for the He and Be atoms, and for the LiH, CH + , and LiF molecules, show that the laser-driven evolution of the stationary-state populations at the coupled-cluster singles-and-doubles (CCSD) level is very close to that obtained by full configurationinteraction theory provided all stationary states actively participating in the dynamics are sufficiently well approximated. When double-excited states are important for the dynamics, the quality of the CCSD results deteriorate. Observing that populations

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Section: Conservation Lawsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Interpretation of Coupled-Cluster Many-Electron Dynamics in Terms of Stationary States

Pedersen,

Kristiansen,

Bodenstein

et al. 2020

Preprint

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“…Most methods which can describe the electron dynamics are often modified versions of their well-known quantumchemical counter parts and neglect the influence of the nuclear motion [19][20][21][22][23] or treat it classically [24][25][26][27]. One of the possibilities to treat both the nuclear and the electron dynamics in a molecular systems is the quantum-mechanical NEMol ansatz [28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Photo-Induced Coupled Nuclear and Electron Dynamics in the Nucleobase Uracil

et al. 2021

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Photo-initiated processes in molecules often involve complex situations where the induced dynamics is characterized by the interplay of nuclear and electronic degrees of freedom. The interaction of the molecule with an ultrashort laser pulse or the coupling at a conical intersection (CoIn) induces coherent electron dynamics which is subsequently modified by the nuclear motion. The nuclear dynamics typically leads to a fast electronic decoherence but also, depending on the system, enables the reappearance of the coherent electron dynamics. We study this situation for the photo-induced nuclear and electron dynamics in the nucleobase uracil. The simulations are performed with our ansatz for the coupled description of the nuclear and electron dynamics in molecular systems (NEMol). After photo-excitation uracil exhibits an ultrafast relaxation mechanism mediated by CoIn's. Both processes, the excitation by a laser pulse and the non-adiabatic relaxation, are explicitly simulated and the coherent electron dynamics is monitored using our quantum mechanical NEMol approach. The electronic coherence induced by the CoIn is observable for a long time scale due to the delocalized nature of the nuclear wavepacket.

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“…Most approaches use time-dependent analogs of well-established quantumchemical methods like time-dependent Hartree-Fock theory (TD-HF) 9 or time-dependent density-functional theory (TD-DFT) 10 . Furthermore, time-dependent post-Hartree-Fock methods like time-dependent configuration-interaction (TD-CI) 11,12 , time-dependent coupled-cluster (TD-CC) 13,14 and multi-configuration time-dependent Hartree-Fock 15 are available for the correlated description of electron dynamics in molecular systems. In other theoretical approaches the electronic wavefunction is propagated directly in time, with the help of Green's function 16 or in the basis of molecular orbitals 17 .…”

Section: Introductionmentioning

confidence: 99%

Coupled nuclear and electron dynamics in the vicinity of a conical intersection

Schnappinger,

de Vivie-Riedle

2021

Preprint

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Ultrafast optical techniques allow to study ultrafast molecular dynamics involving both nuclear and electronic motion. To support interpretation, theoretical approaches are needed that can describe both the nuclear and electron dynamics. Hence, we revisit and expand our ansatz for the coupled description of the nuclear and electron dynamics in molecular systems (NEMol). In this purely quantum mechanical ansatz the quantum-dynamical description of the nuclear motion is combined with the calculation of the electron dynamics in the eigenfunction basis. The NEMol ansatz is applied to simulate the coupled dynamics of the molecule NO 2 in the vicinity of a conical intersection (CoIn) with a special focus on the coherent electron dynamics induced by the non-adiabatic coupling. Furthermore, we aim to control the dynamics of the system when passing the CoIn. The control scheme relies on the carrier envelope phase (CEP) of a few-cycle IR pulse. The laser pulse influences both the movement of the nuclei and the electrons during the population transfer through the CoIn.

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Time-dependent coupled-cluster theory for ultrafast transient-absorption spectroscopy

Cited by 24 publications

References 39 publications

Interpretation of Coupled-Cluster Many-Electron Dynamics in Terms of Stationary States

Interpretation of Coupled-Cluster Many-Electron Dynamics in Terms of Stationary States

Photo-Induced Coupled Nuclear and Electron Dynamics in the Nucleobase Uracil

Coupled nuclear and electron dynamics in the vicinity of a conical intersection

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