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Ab initio nonadiabatic dynamics involving conical intersection combined with Wigner distribution approach to ultrafast spectroscopy illustrated on Na3F2 cluster

  • We present a theoretical study of a femtosecond photo isomerization process due to a nonadiabatic radiationless decay from the first excited state through a conical intersection occurring in one of the nonstoichiometric halide-deficient clusters with one excess electron (Na3F2). This is an extension of the adiabatic dynamics study presented in the accompanying paper [J. Chem. Phys. 114, 2106 (2001)] for other members of the NanFn−1 series characterized by a strong ionic bonding for which the “frozen ionic bonds” approximation has been justified, allowing consideration of the optical response of the single excess electron in the effective field of the other electrons. In this contribution we outline the extension of the ab initio Wigner-distribution approach to nonadiabatic molecular dynamics which combines the Wigner–Moyal representation of the vibronic density matrix with the ab initio multistate molecular dynamics in the ground- and excited electronic states including the nonadiabatic coupling computed “on the fly” in connectionWe present a theoretical study of a femtosecond photo isomerization process due to a nonadiabatic radiationless decay from the first excited state through a conical intersection occurring in one of the nonstoichiometric halide-deficient clusters with one excess electron (Na3F2). This is an extension of the adiabatic dynamics study presented in the accompanying paper [J. Chem. Phys. 114, 2106 (2001)] for other members of the NanFn−1 series characterized by a strong ionic bonding for which the “frozen ionic bonds” approximation has been justified, allowing consideration of the optical response of the single excess electron in the effective field of the other electrons. In this contribution we outline the extension of the ab initio Wigner-distribution approach to nonadiabatic molecular dynamics which combines the Wigner–Moyal representation of the vibronic density matrix with the ab initio multistate molecular dynamics in the ground- and excited electronic states including the nonadiabatic coupling computed “on the fly” in connection with the fewest-switches hopping algorithm. This scheme allows accounting for temperature-dependent initial conditions, for the propagation in the excited state and in the ground state after the passage through the conical intersection, and for probing in the cationic ground state as well as for deriving analytic expressions for the pump–probe signals which utilize an ensemble of classical trajectories obtained at low computational demand. Our approach permits investigation of the photo isomerization through the conical intersection due to the long amplitude motion in the Na3F2 system in full complexity, taking into account all degrees of freedom. After breaking of one metallic and of one ionic bond the conical intersection occurs at the linear geometry and involves states of different symmetry which differ in the translocation of the one excess electron or positive charge localized at the Na atom from one end to the other of the system and separates two isomers with Cs and C2v structures. From the analysis of the nonadiabaticdynamics, the time scales for the metallic bond breaking of ∼90 fs and for the ionic bond breaking of ∼220 fs, for the passage through the conical intersection after ∼0.4 ps and for the internal vibrational energy redistribution (IVR) of more than 0.9 ps for the individual isomers, have been determined. The simulated fs pump–probe signals confirm the above results and provide the information about the experimental conditions such as laser frequencies and pulse duration under which bond breaking of different type as well as the population of each of the two isomers after the passage through the conical intersection can be identified. In this contribution we show that the mechanism of the photo isomerization at a conical intersection due to a long amplitude motion can occur in atomic clusters and is not necessarily limited to organic photochemistry.show moreshow less
Metadaten
Author:Prof. Dr. Michael Hartmann, Jiřı́ Pittner, Vlasta Bonačić-Koutecký
Parent Title (English):The Journal of Chemical Physics
Document Type:Article
Language:English
Date of Publication (online):2014/07/02
Year of first Publication:2001
Publishing Institution:SRH Berlin University of Applied Sciences
Release Date:2014/07/02
Tag:Chemical physics; Wigner distribution
Volume:114
Issue:5
First Page:2123
Last Page:2136
Note:
Volltext aus urheberrechtlichen Gründen nicht verfügbar.
Fulltext due to copyright not available.
Link author profile:https://www.srh-berlin.de/hochschule/hochschulteam/hartmann-michael/
Peer-reviewed:Keine Angabe - No details
JEL-Classification:Y Miscellaneous Categories
Licence (German):License LogoCreative Commons - Namensnennung-Nicht kommerziell-Keine Bearbeitung
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