An “optimal” spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics

Yang, Sandy; Coe, Joshua D.; Kaduk, Benjamin; Martı́nez, Todd J.

doi:10.1063/1.3103930

Cited by 90 publications

(96 citation statements)

References 88 publications

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“…Indeed, under the same initial conditions as the current study, using our present analytical coupling code but with momentum adjustment along the energy difference gradient (as done in the previous study) the excitedstate lifetime was increased by about 10%. This is expected since the spawned basis functions will tend to have lower (in magnitude) Hamiltonian matrix elements with the parent TBF for momentum The Journal of Physical Chemistry A ARTICLE a d j u s t m e n t st h a ta r en o ta l o n gt h e nonadiabatic coupling vector 34 (this is the essence of the semiclassical argument 35 for using the nonadiabatic coupling vector as the momentum adjustment direction in surface hopping).…”

Section: Resultsmentioning

confidence: 99%

“…In AIMS, this flexibility is attained by adaptively increasing the number of TBFs, in a process called spawning, when the coupling of two states rises above a predefined threshold. As discussed in detail previously, 15,31,34 the nonadiabatic coupling vectors are used in AIMS in three ways: (1) to construct the Hamiltonian matrix elements in eq 5, (2) to decide when spawning occurs, and (3) to determine the momentum of the newly created child TBF's following spawning. In the first two uses, one does not need the entire nonadiabatic coupling vector but rather only the dot product with a (complex) off-diagonal matrix element of the momentum operator.…”

Section: Theoretical Methodsmentioning

confidence: 99%

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Role of Rydberg States in the Photochemical Dynamics of Ethylene

et al. 2012

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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. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/jp2097185Access and use of this website and the material on it are subject to the Terms and Conditions set forth atThe role of Rydberg states in the photochemical dynamics of ethylene Mori, Toshifumi; Glover, William J.; Schuurman, Michael S.; Martinez, Todd J.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

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Section: Resultsmentioning

confidence: 99%

Section: Theoretical Methodsmentioning

confidence: 99%

Role of Rydberg States in the Photochemical Dynamics of Ethylene

et al. 2012

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“…This behavior contrasts with that of the spin-diabatic TSH dynamics, where a large number of hops between states are observed. 13 As discussed in detail in the AIMS literature, 22,35 improving the spawning criterion would surely result in an even better match with the exact result. We intend to investigate potential improvements in the spawning criteria for ISC in future research.…”

Section: Test Applicationsmentioning

confidence: 97%

“…For detailed discussions about the spawning algorithm between same-spin states, the reader is referred to previous works. 22,24,35 In GFMS, the spawning algorithm needs to be extended to allow for spawning between spinorbit coupled states. Based on an already proposed effective coupling between diabatic states, 22 we suggest to measure the effective SOC strength between state I and state J at the position of TBF k as…”

Section: Theorymentioning

confidence: 99%

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Curchod

Rauer

Marquetand

et al. 2016

The Journal of Chemical Physics

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104

103

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A new approach to molecular dynamics with non-adiabatic and spin-orbit effects with applications to QM/MM simulations of thiophene and selenophene The Journal of Chemical Physics 146, 114101 (2017); 10.1063/1.4978289 THE JOURNAL OF CHEMICAL PHYSICS 144, 101102 (2016) Communication: GAIMS-Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes Full multiple spawning is a formally exact method to describe the excited-state dynamics of molecular systems beyond the Born-Oppenheimer approximation. However, it has been limited until now to the description of radiationless transitions taking place between electronic states with the same spin multiplicity. This Communication presents a generalization of the full and ab initio multiple spawning methods to both internal conversion (mediated by nonadiabatic coupling terms) and intersystem crossing events (triggered by spin-orbit coupling matrix elements) based on a spin-diabatic representation. The results of two numerical applications, a model system and the deactivation of thioformaldehyde, validate the presented formalism and its implementation. C 2016 AIP Publishing LLC. [http://dx

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“…Nevertheless an ab initio on-the-fly direct dynamics version of vMCG does exist. 33 The AIMS 10,24,[34][35][36] method uses a much simpler choice for the evolution of the TBFs: their phase space centers evolve classically on a specific electronic state and the basis set is expanded adaptively as needed, in a process called spawning. The spawning becomes particularly important near the intersection with another electronic state, where more Gaussians are spawned on the second PES.…”

Section: Introductionmentioning

confidence: 99%

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Makhov

Glover

Martı́nez

et al. 2014

The Journal of Chemical Physics

205

245

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An atomic orbital-based formulation of analytical gradients and nonadiabatic coupling vector elements for the state-averaged complete active space self-consistent field method on graphical processing units We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as "cloning," in analogy to the "spawning" procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, "trains," as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.

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An “optimal” spawning algorithm for adaptive basis set expansion in nonadiabatic dynamics

Cited by 90 publications

References 88 publications

Role of Rydberg States in the Photochemical Dynamics of Ethylene

Role of Rydberg States in the Photochemical Dynamics of Ethylene

Communication: GAIMS—Generalized Ab Initio Multiple Spawning for both internal conversion and intersystem crossing processes

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

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