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Light-induced molecular dynamics often involve the excitation of several electronic, vibrational, and rotational states. Since the ensuing electronic and nuclear motion determines the pathways and outcomes of photoinduced reactions, our…

Nonadiabatic phenomena are investigated in the rovibrational motion of molecules confined in an infrared cavity. Conical intersections (CIs) between vibrational polaritons, similar to CIs between electronic polaritonic surfaces, are found.…

Quantum Physics · Physics 2021-02-24 Tamás Szidarovszky , Péter Badankó , Gábor J. Halász , Ágnes Vibók

Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of…

Chemical Physics · Physics 2024-04-11 Nikolay V. Golubev , Jiří Vaníček

Conical intersections (CoIn) dominate the pathways and outcomes of virtually all photophysical and photochemical molecular processes. Despite extensive experimental and theoretical effort, CoIns have not been directly observed yet and the…

Chemical Physics · Physics 2015-11-16 Markus Kowalewski , Kochise Bennett , Konstantin E. Dorfman , Shaul Mukamel

Nonadiabatic molecular dynamics is an effective method for modeling nonradiative decay in electronically excited molecules. Its accuracy depends strongly on the quality of the potential energy surfaces, and its affordability for long…

Chemical Physics · Physics 2024-10-11 Matthew R. Hennefarth , Donald G. Truhlar , Laura Gagliardi

The motion of electrons and nuclei in photochemical events often involve conical intersections, degeneracies between electronic states. They serve as funnels for nuclear relaxation - on the femtosecond scale - in processes where the…

Chemical Physics · Physics 2017-08-14 Eirik F. Kjønstad , Henrik Koch

The interaction between nuclei and a strong zeptosecond laser pulse with coherent MeV photons is investigated theoretically. We provide a first semi-quantitative study of the quasiadiabatic regime where the photon absorption rate is…

Nuclear Theory · Physics 2016-02-22 Adriana Pálffy , Oliver Buss , Axel Hoefer , Hans A. Weidenmüller

A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new…

Chemical Physics · Physics 2018-04-04 Loïc Joubert-Doriol , Artur F. Izmaylov

The interaction between electronic and vibrational degrees of freedom is an important mechanism in nonequilibrium charge transport through molecular nanojunctions. While adiabatic polaron-type coupling has been studied in great detail, new…

Mesoscale and Nanoscale Physics · Physics 2022-06-10 Christoph Kaspar , André Erpenbeck , Jakob Bätge , Christian Schinabeck , Michael Thoss

We discuss nuclear dynamics at molecule-metal interfaces including non-equilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we…

Mesoscale and Nanoscale Physics · Physics 2015-11-30 Michael Galperin , Abraham Nitzan

An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…

Chemical Physics · Physics 2016-07-27 Alexander Humeniuk , Roland Mitrić

A dynamical rearrangement in the electronic structure of a molecule can be driven by different phenomena, including nuclear motion, electronic coherence or electron correlation. Recording such electronic dynamics and identifying their fate…

Attosecond charge migration is a periodic evolution of the charge density of a molecule on a time scale defined by the energy intervals between the electronic states involved. Here, we report the observation of charge migration in neutral…

Multi-dimensional spectroscopy represents a particularly insightful tool for investigating the interplay of nuclear and electronic dynamics, which plays an important role in a number of photophysical processes and photochemical reactions.…

Quantum Physics · Physics 2022-07-26 Frank Ernesto Quintela Rodriguez , Filippo Troiani

Ultrafast laser excitation can trigger multiplex coherent dynamics in molecules. Here, we report attosecond transient absorption experiments addressing simultaneous probing of electronic and vibrational dynamics in a prototype molecule,…

We introduce multistate metadynamics for automatic exploration of conical intersection seams between adiabatic Born-Oppenheimer potential energy surfaces in molecular systems. By choosing the energy gap between the electronic states as a…

Chemical Physics · Physics 2018-05-10 Joachim O. Lindner , Merle I. S. Röhr , Roland Mitrić

The electronic and nuclear dynamics in methanol, following 156~nm photoexcitation, are investigated by combining a detailed analysis of time-resolved photoelectron spectroscopy experiments with electronic structure calculations. The…

Ultrafast photoinduced dynamics of electronic excitation in molecular dimers is drastically affected by the dynamic reorganization of inter- and intra- molecular nuclear configuration modeled by a quantized nuclear degree of freedom [Cina…

Mathematical Physics · Physics 2009-11-10 Dmitri S. Kilin , Yuri V. Pereversev , Oleg V. Prezhdo

We present a means of studying rare reactive pathways in open quantum systems using Transition Path Theory and ensembles of quantum jump trajectories. This approach allows for elucidation of reactive paths for dissipative, nonadiabatic…

Chemical Physics · Physics 2022-11-09 Michelle C. Anderson , Addison J. Schile , David T. Limmer