BEYOND BORN-OPPENHEIMER: Molecular Dynamics Through a Conical Intersection

Worth, Graham A.; Cederbaum, Lorenz S.

doi:10.1146/annurev.physchem.55.091602.094335

Cited by 767 publications

(765 citation statements)

References 93 publications

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“…Conical intersections (CIs) between electronic potential energy surfaces play a key mechanistic role in various basic molecular processes [1][2][3][4]. In this case the electronic states are coupled by the nuclear motion, and the energy exchange between the fast electrons and the slow nuclei becomes significant.…”

Section: Introductionmentioning

confidence: 99%

Nuclear-wave-packet quantum interference in the intense laser dissociation of the D2+molecule

et al. 2013

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Recently it has been recognized that electronic conical intersections in molecular systems can be induced by laser light even in diatomics. As is known a direct consequence of these accidental degeneracies is the appearance of nonadiabatic effects which has a strong impact on the nuclear quantum dynamics. Studying the photodissociation process of the D 2 + molecule, we report here some observable quantum interference phenomena that arise from the topological singularity induced by a strong laser field.

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Section: Introductionmentioning

confidence: 99%

Nuclear-wave-packet quantum interference in the intense laser dissociation of the D2+molecule

et al. 2013

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“…In spite of its simplicity, H LVC parametrized with ab initio methods produced quite accurate results for vibronic spectra and dynamics in many molecules. 1,12,13 However, the LVC Hamiltonian does not have an analytical solution and still would require quite involved quantum dynamical simulations to obtain population dynamics. 14 In order to reduce the computational cost for large systems, one can consider only a restricted number of nuclear DOF which are the most relevant to the electronic transition.…”

Section: Introductionmentioning

confidence: 99%

Nonequilibrium Fermi golden rule for electronic transitions through conical intersections

Izmaylov

Mendive-Tapia²,

Bearpark³

et al. 2011

The Journal of Chemical Physics

108

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We consider photoinduced electronic transitions through conical intersections in large molecules.Starting from the linear vibronic model Hamiltonian and treating linear diabatic couplings within the second order cumulant expansion we have developed a simple analytical expression for the time evolution of electronic populations at finite temperature. The derived expression can be seen as a nonequilibrium generalization of the Fermi Golden Rule due to a nonequilibrium character of the initial photoinduced nuclear distribution. All parameters in our model are obtained from electronic structure calculations followed by a diabatization procedure. The results of our model are found to agree well with those of quantum dynamics for a test set of systems: fulvene molecule, bis-methylene adamantane cation and its dimethyl derivative.

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“…Thus accurate methods to compute the nuclear quantum dynamics in systems with up to 20-30 degrees of freedom have already been developed (see e.g. the review [106]), but the interplay with the electron dynamics still relies on important simplifications such as the local approximation [107,108]. Therefore the challenge for the next few years is to go beyond these approximations in polyatomic molecules, which will lead to a better understanding of the role of dissociative ionization processes in such complex systems.…”

Section: Discussionmentioning

confidence: 99%

Molecular ionization and dissociation using synchrotron radiation and ultrashort laser pulses

Martín¹

2007

J. Phys.: Conf. Ser.

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Abstract. An overview of recent theoretical progress to accurately describe non dissociative and dissociative ionization of molecules exposed to synchrotron radiation and ultrashort uv/xuv laser pulses is presented. The success of recent theoretical approaches rely on their ability to account for both the electronic and nuclear degrees of freedom. This is essential to describe the delicate interplay between the electronic motion and the molecule's vibration, especially in those cases where ionization occurs in a time scale comparable to that of the vibrational motion. Some of the most successful applications and the new physics that has emerged by comparing with recent kinematically complete experiments on H2 and D2 will be discussed. IntroductionMolecular ionization is one of the most elementary processes that occurs in the upper atmosphere [1] and in interstellar molecular clouds [2]. Since in molecules the absorbed energy is shared between electronic and nuclear degrees of freedom, the remaining molecular ion can be left in an excited vibrational or dissociative state. This is at variance with atomic ionization where the energy is entirely absorbed by the electrons. In early pictures of molecular ionization, the nuclear motion was either ignored or described in terms of the Franck-Condon (FC) approximation, in which electronic processes occurring at the equilibrium position of the nuclei are weighted by the squared overlap between the initial and final vibrational states. With the advent of kinematically complete experiments [3,4], in which the momenta of all charged particles is determined, new phenomena with an intrinsic molecular origin have been discovered (see, e.g., [5][6][7][8][9][10][11]). Also the above pictures have been revealed to be incomplete. In this manuscript, the important role of nuclear dynamics in molecular ionization produced by synchrotron radiation and ultrashort pulses will be demonstrated by means of recent ab initio theoretical calculations that account for all electronic and vibrational degrees of freedom.In particular, recent results for electron angular distributions from fixed-in-space molecules will be analyzed and compared with kinematically complete photoionization experiments using synchrotron radiation. These include double and single photoionization of H 2 (D 2 ). The range of excess photon energies considered goes from a few to several hundreds of eV. Also, multiphoton ionization of molecules by vuv ultrashort pulses will be discussed. In particular, the new physics that can be expected by varying pulse duration and intensity will be analyzed.

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BEYOND BORN-OPPENHEIMER: Molecular Dynamics Through a Conical Intersection

Cited by 767 publications

References 93 publications

Nuclear-wave-packet quantum interference in the intense laser dissociation of the D2+molecule

Nuclear-wave-packet quantum interference in the intense laser dissociation of the D2+molecule

Nonequilibrium Fermi golden rule for electronic transitions through conical intersections

Molecular ionization and dissociation using synchrotron radiation and ultrashort laser pulses

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