Photoinduced nonadiabatic dynamics of ethene: Six-dimensional wave packet propagations using two different approximations of the kinetic energy operator

Brill, Michael; Gatti, Fabien; Lauvergnat, David; Meyer, Hans‐Dieter

doi:10.1016/j.chemphys.2007.04.002

Cited by 32 publications

(46 citation statements)

References 37 publications

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“…(111,C4) numerically. We have verified that the numerical values of all the functions G ij (q) at several non-symmetrical grid points q agree with those provided by the program TNUM for systems such as C 2 H 4 [126], HCF 3 in valence coordinates [127] or the Zundel cation, H 5 O + 2 , in Jacobi coordinates [128] or in mixed Jacobi/valence coordinates (in all cases for J = 0). The latter test does not only guarantee that the KEO is correct but also that the operator is correctly implemented in the code used to solve the Schrödinger equation, in this case the Heidelberg MCTDH package [129].…”

Section: E Checking the Correctness Of The Operatorssupporting

confidence: 62%

Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach

Gatti¹,

Iung²

2008

Journal of End-to-End-testing

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HAL is a multi-disciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.

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Section: E Checking the Correctness Of The Operatorssupporting

confidence: 62%

Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach

Gatti¹,

Iung²

2008

Journal of End-to-End-testing

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“…The excited-state dynamics of this prototypical molecule for double bond isomerization has been studied by a range of methods. 143,201,203,[205][206]213,[292][293][294][295][296] When combined with MS-CASPT2, 201 AIMS offers unprecedented accuracy to describe the excited-state dynamics and the lifetime of ethylene upon photoexcitation to its * electronic state. 206 Figure 14).…”

Section: Ab Initio Multiple Spawningmentioning

confidence: 99%

Ab Initio Nonadiabatic Quantum Molecular Dynamics

2018

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The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born-Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump-probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third class of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.

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“…13,28 Note that this program has also recently been used to check the correctness of analytically derived KEOs in MCTDH calculations. 5,39 In the following we give a brief review of the basic equations needed in context of KEOs within curvilinear coordinates, where, for the sake of simplicity, we restrict ourselves to the case of zero total angular momentum (J = 0).…”

Section: E Numerical Kinetic Energy Operatormentioning

confidence: 99%

Quantum-mechanical wavepacket propagation in a sparse, adaptive basis of interpolating Gaussians with collocation

Sielk

Horsten

Krüger

et al. 2009

Phys. Chem. Chem. Phys.

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We present an extension of our earlier work on adaptive quantum wavepacket dynamics [B. Hartke, Phys. Chem. Chem. Phys., 2006, 8, 3627]. In this dynamically pruned basis representation the wavepacket is only stored at places where it has non-negligible contributions. Here we enhance the former 1D proof-of-principle implementation to higher dimensions and optimize it by a new basis set, interpolating Gaussians with collocation. As a further improvement the TNUM approach from Lauvergnat and Nauts [J. Chem. Phys., 2002, 116, 8560] was implemented, which in combination with our adaptive representation offers the possibility of calculating the whole Hamiltonian on-the-fly. For a two-dimensional artificial benchmark and a three-dimensional real-life test case, we show that a sparse matrix implementation of this approach saves memory compared to traditional basis representations and comes even close to the efficiency of the fast Fourier transform method. Thus we arrive at a quantum wavepacket dynamics implementation featuring several important black-box characteristics: it can treat arbitrary systems without code changes, it calculates the kinetic and potential part of the Hamiltonian on-the-fly, and it employs a basis that is automatically optimized for the ongoing wavepacket dynamics.

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Photoinduced nonadiabatic dynamics of ethene: Six-dimensional wave packet propagations using two different approximations of the kinetic energy operator

Cited by 32 publications

References 37 publications

Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach

Exact and constrained kinetic energy operators for polyatomic molecules: The polyspherical approach

Ab Initio Nonadiabatic Quantum Molecular Dynamics

Quantum-mechanical wavepacket propagation in a sparse, adaptive basis of interpolating Gaussians with collocation

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