Dissipative dynamics of a system passing through a conical intersection: Ultrafast pump-probe observables

David Gelman, Gil Katz, Ronnie Kosloff, Mark A Ratner

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

The dynamics of a system incorporating a conical intersection, in the presence of a dissipative environment, is studied with the purpose of identifying observable ultrafast spectroscopic signatures. A model system consisting of two vibronically coupled electronic states with two nuclear degrees of freedom is constructed. Dissipation is treated by two different methods, Lindblad semigroup formalism and the surrogate Hamiltonian approach. Pump-probe experimental expectation values such as transient emission and transient absorption are calculated and compared to the adiabatic and diabatic population transfer. The ultrafast population transfer reflecting the conical intersection is not mirrored in transient absorption measurements such as the recovery of the bleach. Emission from the excited state can be suppressed on the ultrafast time scale, but the existence of a conical intersection is only one of the possible mechanisms that can provide ultrafast damping of emission.

Original languageEnglish
Article number134112
JournalJournal of Chemical Physics
Volume123
Issue number13
DOIs
Publication statusPublished - Oct 3 2005

Fingerprint

intersections
Pumps
pumps
probes
Hamiltonians
Electronic states
Excited states
dissipation
degrees of freedom
Damping
damping
recovery
signatures
formalism
Recovery
electronics
excitation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Dissipative dynamics of a system passing through a conical intersection : Ultrafast pump-probe observables. / Gelman, David; Katz, Gil; Kosloff, Ronnie; Ratner, Mark A.

In: Journal of Chemical Physics, Vol. 123, No. 13, 134112, 03.10.2005.

Research output: Contribution to journalArticle

@article{68b16df3aeb445ceac9696f22473f936,
title = "Dissipative dynamics of a system passing through a conical intersection: Ultrafast pump-probe observables",
abstract = "The dynamics of a system incorporating a conical intersection, in the presence of a dissipative environment, is studied with the purpose of identifying observable ultrafast spectroscopic signatures. A model system consisting of two vibronically coupled electronic states with two nuclear degrees of freedom is constructed. Dissipation is treated by two different methods, Lindblad semigroup formalism and the surrogate Hamiltonian approach. Pump-probe experimental expectation values such as transient emission and transient absorption are calculated and compared to the adiabatic and diabatic population transfer. The ultrafast population transfer reflecting the conical intersection is not mirrored in transient absorption measurements such as the recovery of the bleach. Emission from the excited state can be suppressed on the ultrafast time scale, but the existence of a conical intersection is only one of the possible mechanisms that can provide ultrafast damping of emission.",
author = "David Gelman and Gil Katz and Ronnie Kosloff and Ratner, {Mark A}",
year = "2005",
month = "10",
day = "3",
doi = "10.1063/1.2032968",
language = "English",
volume = "123",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "13",

}

TY - JOUR

T1 - Dissipative dynamics of a system passing through a conical intersection

T2 - Ultrafast pump-probe observables

AU - Gelman, David

AU - Katz, Gil

AU - Kosloff, Ronnie

AU - Ratner, Mark A

PY - 2005/10/3

Y1 - 2005/10/3

N2 - The dynamics of a system incorporating a conical intersection, in the presence of a dissipative environment, is studied with the purpose of identifying observable ultrafast spectroscopic signatures. A model system consisting of two vibronically coupled electronic states with two nuclear degrees of freedom is constructed. Dissipation is treated by two different methods, Lindblad semigroup formalism and the surrogate Hamiltonian approach. Pump-probe experimental expectation values such as transient emission and transient absorption are calculated and compared to the adiabatic and diabatic population transfer. The ultrafast population transfer reflecting the conical intersection is not mirrored in transient absorption measurements such as the recovery of the bleach. Emission from the excited state can be suppressed on the ultrafast time scale, but the existence of a conical intersection is only one of the possible mechanisms that can provide ultrafast damping of emission.

AB - The dynamics of a system incorporating a conical intersection, in the presence of a dissipative environment, is studied with the purpose of identifying observable ultrafast spectroscopic signatures. A model system consisting of two vibronically coupled electronic states with two nuclear degrees of freedom is constructed. Dissipation is treated by two different methods, Lindblad semigroup formalism and the surrogate Hamiltonian approach. Pump-probe experimental expectation values such as transient emission and transient absorption are calculated and compared to the adiabatic and diabatic population transfer. The ultrafast population transfer reflecting the conical intersection is not mirrored in transient absorption measurements such as the recovery of the bleach. Emission from the excited state can be suppressed on the ultrafast time scale, but the existence of a conical intersection is only one of the possible mechanisms that can provide ultrafast damping of emission.

UR - http://www.scopus.com/inward/record.url?scp=26444580201&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=26444580201&partnerID=8YFLogxK

U2 - 10.1063/1.2032968

DO - 10.1063/1.2032968

M3 - Article

AN - SCOPUS:26444580201

VL - 123

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 13

M1 - 134112

ER -