Expressions for linear and nonlinear spectroscopy simulation in the X-ray window in which the time evolution of a photoexcited molecular system is treated via quantum dynamics are derived. By leveraging on the peculiar properties of core-excited/ionized states, first- and third-order response functions are recast in the limit of time-scale separation between the extremely short core-state lifetime and the (comparably longer) electronic-state transfer and nuclear vibrational motion. This work is a natural extension of Segatta et al. (J. Chem. Theory Comput. 2023, 19, 2075-2091), in which some of the present authors coupled MCTDH quantum dynamics to spectroscopy simulation at different levels of sophistication. Full quantum dynamics and approximate expressions are compared by simulating X-ray transient absorption spectroscopy at the carbon K-edge in the pyrene molecule.

Segatta F., Aranda D., Aleotti F., Montorsi F., Mukamel S., Garavelli M., et al. (2023). Time-Resolved X-ray Absorption Spectroscopy: An MCTDH Quantum Dynamics Protocol. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 20(1), 307-322 [10.1021/acs.jctc.3c00953].

Time-Resolved X-ray Absorption Spectroscopy: An MCTDH Quantum Dynamics Protocol

Segatta F.;Aleotti F.;Montorsi F.;Garavelli M.
;
Nenov A.
2023

Abstract

Expressions for linear and nonlinear spectroscopy simulation in the X-ray window in which the time evolution of a photoexcited molecular system is treated via quantum dynamics are derived. By leveraging on the peculiar properties of core-excited/ionized states, first- and third-order response functions are recast in the limit of time-scale separation between the extremely short core-state lifetime and the (comparably longer) electronic-state transfer and nuclear vibrational motion. This work is a natural extension of Segatta et al. (J. Chem. Theory Comput. 2023, 19, 2075-2091), in which some of the present authors coupled MCTDH quantum dynamics to spectroscopy simulation at different levels of sophistication. Full quantum dynamics and approximate expressions are compared by simulating X-ray transient absorption spectroscopy at the carbon K-edge in the pyrene molecule.
2023
Segatta F., Aranda D., Aleotti F., Montorsi F., Mukamel S., Garavelli M., et al. (2023). Time-Resolved X-ray Absorption Spectroscopy: An MCTDH Quantum Dynamics Protocol. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 20(1), 307-322 [10.1021/acs.jctc.3c00953].
Segatta F.; Aranda D.; Aleotti F.; Montorsi F.; Mukamel S.; Garavelli M.; Santoro F.; Nenov A.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/953432
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