Strong-pump strong-probe spectroscopy: effects of higher excited electronic states

Gelin, Maxim F.; Egorova, Dassia; Domcke, Wolfgang

doi:10.1039/c3cp44454f

Cited by 23 publications

(12 citation statements)

References 74 publications

(81 reference statements)

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“…Numerous papers reported useful simulations of TA spectra using tight-binding (TB) and ab initio models. − TB models are constructed from calculated or experimental energies and properties; the basis states are treated distinguishably. Approximations must be used for energies and couplings, and their accuracy relies on the practitioner.…”

mentioning

confidence: 99%

Black-Box, Real-Time Simulations of Transient Absorption Spectroscopy

Nguyen

Koh

Lefelhocz

et al. 2016

J. Phys. Chem. Lett.

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We introduce an atomistic, all-electron, black-box electronic structure code to simulate transient absorption (TA) spectra and apply it to simulate pyrazole and a GFP-chromophore derivative. The method is an application of OSCF2, our dissipative extension of time-dependent density functional theory. We compare our simulated spectra directly with recent ultrafast spectroscopic experiments. We identify features in the TA spectra to Pauli-blocking, which may be missed without a first-principles model. An important ingredient in this method is the stationary-TDDFT correction scheme recently put forward by Fischer, Govind, and Cramer that allows us to overcome a limitation of adiabatic TDDFT. We demonstrate that OSCF2 is able to reproduce the energies of bleaches and induced absorptions as well as the decay of the transient spectrum with only the molecular structure as input.

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confidence: 99%

Black-Box, Real-Time Simulations of Transient Absorption Spectroscopy

Nguyen

Koh

Lefelhocz

et al. 2016

J. Phys. Chem. Lett.

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“…Ref. 32). Strong-pulse double-slit experiments on systems exhibiting photochemical reactions (e.g., photoinduced electron-transfer or proton-transfer reactions) or on multichromophoric systems should be considered in the future.…”

Section: Discussionmentioning

confidence: 99%

“…While the DW approximation becomes exact for nonoverlapping pulses and the isolated chromophore, this is not necessarily true for the chromophore in solution due to the finite memory induced by the coupling of the chromophore to the bath. Since the validity of the DW approximation is not guaranteed for non-Markovian open systems, 32,41 we did not use it in the actual calculations. The DW approximation is useful, however, for the qualitative interpretation of the signals computed with the HEOM method.…”

Section: Doorway-window Picturementioning

confidence: 99%

“…(B1) is not the final expression for the optical signal: One has to extract the components of D and W which obey the appropriate phase matching condition. 32,40 In the "double slit" experiment, on the other hand, there is no external phase selection. Nonetheless, it is instructive to determine the phase dependence of the signal explicitly.…”

Section: Appendix A: Evaluation Of the Lineshape Functionsmentioning

confidence: 99%

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Simulation of femtosecond “double-slit” experiments for a chromophore in a dissipative environment

Gelin

Tanimura²,

Domcke³

2013

The Journal of Chemical Physics

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We performed simulations of the prototypical femtosecond "double-slit" experiment with strong pulsed laser fields for a chromophore in solution. The chromophore is modeled as a system with two electronic levels and a single Franck-Condon active underdamped vibrational mode. All other (intra- and inter-molecular) vibrational modes are accounted for as a thermal bath. The system-bath coupling is treated in a computationally accurate manner using the hierarchy equations of motion approach. The double-slit signal is evaluated numerically exactly without invoking perturbation theory in the matter-field interaction. We show that the strong-pulse double-slit signal consists of a superposition of N-wave-mixing (N = 2, 4, 6...) responses and can be split into population and coherence contributions. The former reveals the dynamics of vibrational wave packets in the ground state and the excited electronic state of the chromophore, while the latter contains information on the dephasing of electronic coherences of the chromophore density matrix. We studied the influence of heat baths with different coupling strengths and memories on the double-slit signal. Our results show that the double-slit experiment performed with strong (nonperturbative) pulses yields substantially more information on the photoinduced dynamics of the chromophore than the weak-pulse experiment, in particular, if the bath-induced dephasings are fast.

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“…This feature can be used to obtain a fully tailored response from the target system. For laser field intensities too high for perturbation theory to be used, numerical calculations havve been done to understand the novel behavior of the sample due to the high nonlinearity of light-matter interaction [24][25][26][27]. However, this method gives no insight into the general properties of the interaction; thus, analytical models are needed to understand the corresponding dynamics.…”

Section: Introductionmentioning

confidence: 99%

Ultrafast dynamic evolution of multilevel systems in medium-strength laser fields

Wang

Shi

et al. 2019

New J. Phys.

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The ultrafast dynamic evolution of an atomic system under medium-strength laser fields is studied by performing transient absorption measurement. An analytical model developed from perturbation theory with a modified transition dipole moment is presented to explain the spectral features of the multilevel system. By fitting the measured absorption spectra to the model, the system's dynamic evolution is quantified by different amplitude and phase modulation factors in the pump-probe and probe-pump scenarios. This study provides a way to understand laser-matter interaction in the transition area between the strong-field and weak-field regimes.

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Strong-pump strong-probe spectroscopy: effects of higher excited electronic states

Cited by 23 publications

References 74 publications

Black-Box, Real-Time Simulations of Transient Absorption Spectroscopy

Black-Box, Real-Time Simulations of Transient Absorption Spectroscopy

Simulation of femtosecond “double-slit” experiments for a chromophore in a dissipative environment

Ultrafast dynamic evolution of multilevel systems in medium-strength laser fields

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