Multimode Molecular Dynamics Beyond the Born‐Oppenheimer Approximation

Köuppel, H.; Domcke, Wolfgang; Cederbaum, Lorenz S.

doi:10.1002/9780470142813.ch2

Cited by 1,219 publications

(856 citation statements)

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“…Instead, the interplay among electronic and nuclear motions can lead to quite complicated vibronic levels and mixing between electronic and vibrational wavefunctions [34][35][36][37] . This mixing is Box 2…”

Section: Vibronic Coherencementioning

confidence: 99%

Using coherence to enhance function in chemical and biophysical systems

Scholes

Fleming

Chen

et al. 2017

Nature

560

550

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Section: Vibronic Coherencementioning

confidence: 99%

Using coherence to enhance function in chemical and biophysical systems

Scholes

Fleming

Chen

et al. 2017

Nature

560

550

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“…At the same time, the gradient-coupling operator (eq 11) must be evaluated. This operator becomes singular at the CI seam, 40 requiring special care in evaluation of the corresponding matrix elements (see below).…”

Section: ■ Theorymentioning

confidence: 99%

Short-Time Dynamics at a Conical Intersection in High-Harmonic Spectroscopy

Patchkovskii

Schuurman

2014

J. Phys. Chem. A

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Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur.Access and use of this website and the material on it are subject to the Terms and Conditions set forth at Short-time dynamics at a conical intersection in high-harmonic spectroscopy Patchkovskii, Serguei; Schuurman, Michael S.http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/droits L'accès à ce site Web et l'utilisation de son contenu sont assujettis aux conditions présentées dans le site LISEZ CES CONDITIONS ATTENTIVEMENT AVANT D'UTILISER CE SITE WEB. NRC Publications Record / Notice d'Archives des publications de CNRC:http://nparc.cisti-icist.nrc-cnrc.gc.ca/eng/view/object/?id=aad3fd82-4d1b-46b5-8a04-31cbd7427a52 http://nparc.cisti-icist.nrc-cnrc.gc.ca/fra/voir/objet/?id=aad3fd82-4d1b-46b5-8a04-31cbd7427a52 ABSTRACT: High-harmonic spectroscopy probes molecular dynamics using electrons liberated from the same molecule earlier in the laser cycle. It affords sub-Ångstrom spatial and subfemtosecond temporal resolution. Nuclear dynamics in the intermediate cation influence the spectrum of the emitted high-harmonic photons through an autocorrelation function. Here, we develop an analytical approach for computing short-time nuclear autocorrelation functions in the vicinity of conical intersections, including laser-induced and nonadiabatic coupling between the surfaces. We apply the technique to two molecules of current experimental interest, C 6 H 6 and C 6 H 5 F. In both molecules, high-harmonics generated within the same electronic channel are not sensitive to nonadiabatic dynamics, even in the presence of substantial population transfer. Calculated autocorrelation functions exhibit significant deviations from the expected Gaussian decay and may undergo revivals at short (∼1.5 fs) times. The associated phase of the nuclear wavepacket provides a possible experimental signature.

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“…The fitted PES was generated using the VCHAM method [41,43,44], a best-fit expansion in polynomials around the FC point (with additional sine functions along the torsion coordinate in this case 375 to replicate the periodicity of the PES), and with polynomial couplings between modes and states. The GPR method approximates the PES in a similar way to an interpolation, so that the fit to points far away from the FC point is treated on the same 380 footing as the fit at the FC point.…”

mentioning

confidence: 99%

Direct grid-based quantum dynamics on propagated diabatic potential energy surfaces

Richings

Habershon

2017

Chemical Physics Letters

100

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We present a method for performing non-adiabatic, grid-based nuclear quantum dynamics calculations using diabatic potential energy surfaces (PESs) generated "on-the-fly". Gaussian process regression is used to interpolate PESs by using electronic structure energies, calculated at points in configuration space determined by the nuclear dynamics, and diabatising the results using the propagation diabatisation method reported recently [J. Phys. Chem. A, 119, 12457 -12470 (2015)]. To test this new method, the nuclear dynamics on the ground and first electronic excited states of the butatriene cation is studied using a grid-based method. The evolution of diabatic state populations is in very good agreement with those produced using a fitted potential. Overall, our scheme offers a route towards accurate quantum dynamics on diabatic PESs learnt on-the-fly.Keywords: Direct-dynamics, Diabatisation, Grid-based quantum dynamics, Butatriene 2010 MSC: 00-01, 99-00The study of nuclear quantum dynamics of nuclei is of great importance in helping to understand of the time-evolution of molecular systems upon excitation of the electronic degrees-of-freedom (DOFs); such simulations can make direct connections to the states. [6,7] One can model these non-adiabatic transitions using classical mechanics, as in the trajectory surface hopping (TSH) algorithm, [2,[8][9][10] but as the dynamics are inherently quantum mechanical, it is better to use a quantum mechani-25 cal method such as the multi-configuration timedependent Hartree (MCTDH) approach [1, 11,12] where possible.The major bottleneck in performing quantum dynamics calculations is usually not the wavefunc-30 tion time-propagation, but the creation of an appropriate PES on which to run the dynamics. As quantum mechanics is non-local, one needs a PES which is known everywhere in the configuration space of the nuclear motion prior to running the 35 dynamics. For the fully quantum mechanical study of non-adiabatic systems it is usually necessary to convert the PESs from the adiabatic representation to a diabatic representation. The adiabatic representation of the potential is an energy-ordered set 40 of PESs, and corresponds to the energies generated by electronic structure programs. However, at points in configuration space where adiabatic surfaces become degenerate, such as at conical interePreprint submitted to Chemical Physics Letters December 20, 2016 sections (CIs), there is a discontinuity in the gradi-45 ent of the states, such that the adiabatic states are no longer smooth; furthermore, the coupling between the states at these points is also infinite. Neither property of the adiabatic PESs is conducive to performing wavepacket dynamics, so transforma-50 tion to the diabatic representation is performed, resulting in smoothly varying surfaces with finite couplings. Diabatic representations are not unique for a given set of adiabatic states, so an appropriate diabatisation scheme must be chosen before the 55 PES can be used in a dynamics calculation. PESs are usua...

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Multimode Molecular Dynamics Beyond the Born‐Oppenheimer Approximation

Cited by 1,219 publications

References 309 publications

Using coherence to enhance function in chemical and biophysical systems

Using coherence to enhance function in chemical and biophysical systems

Short-Time Dynamics at a Conical Intersection in High-Harmonic Spectroscopy

Direct grid-based quantum dynamics on propagated diabatic potential energy surfaces

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