Improved on-the-Fly MCTDH Simulations with Many-Body-Potential Tensor Decomposition and Projection Diabatization

Richings, Gareth W.; Robertson, Christopher; Habershon, Scott

doi:10.1021/acs.jctc.8b00819

Cited by 39 publications

(109 citation statements)

References 68 publications

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“…Three-state (ν 6a , ν 10a ), (ν 1 , ν 4 ), [34,40,17], [15,18,10], (42,48), (26,24), (ν 9a , ν 3 , ν 8b ), (ν 8a , ν5) [20,22,11], [21,25,10] (20,14,22), (30,14) of primitive and SPF basis functions used in the calculations for the two-state and three-state models are given in Table I. In each calculation, the initial condition for the time propagation was constructed by vertical excitation, i.e., by the transfer of the vibrational ground state of the S 0 state to the diabatic B 2u (ππ * ) electronic state.…”

Section: Combinations Of Modes Numbers Of Spfs Numbers Of Grid Pointsmentioning

confidence: 99%

“…Very recently, it has been shown that the MCTDH method can be implemented without the prior computation of global electronic PESs using machine learning techniques. 20,21 There exist nonadiabatic quantum molecular dynamics methods which bypass the computation of PESs, 9 such as the ab initio multiple spawning (AIMS) method 2,[22][23][24] and direct-dynamics versions of the variational multi-configurational Gaussian (vMCG) method. 25,26 These methods are gaining increasing popularity.…”

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confidence: 99%

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Assessing the performance of trajectory surface hopping methods: Ultrafast internal conversion in pyrazine

Xie

Sapunar

Došlić

et al. 2019

The Journal of Chemical Physics

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Trajectory surface hopping (TSH) methods have been widely used to study photoinduced nonadiabatic processes. In the present study, nonadiabatic dynamics simulations with the widely used Tully's fewest switches surface hopping (FSSH) algorithm and a Landau-Zener-type TSH (LZSH) algorithm have been performed for the internal conversion dynamics of pyrazine. The accuracy of the two TSH algorithms has been critically evaluated by a direct comparison with exact quantum dynamics calculations for a model of pyrazine. The model comprises the three lowest excited electronic states (B 3u (nπ *), A 1u (nπ *), and B 2u (ππ *)) and the nine most relevant vibrational degrees of freedom. Considering photoexcitation to the diabatic B 2u (ππ *) state, we examined the time-dependent diabatic and adiabatic electronic population dynamics. It is found that the diabatic populations obtained with both TSH methods are in good agreement with the exact quantum results. Fast population oscillations between the B 3u (nπ *) and A 1u (nπ *) states, which reflect nonadiabatic electronic transitions driven by coherent dynamics in the normal mode Q 8a , are qualitatively reproduced by both TSH methods. In addition to the model study, the TSH methods have been interfaced with the second-order algebraic diagrammatic construction ab initio electronic-structure method to perform full-dimensional onthe-fly nonadiabatic dynamics simulations for pyrazine. It is found that the electronic population dynamics obtained with the LZSH method is in excellent agreement with that obtained by the FSSH method using a local diabatization algorithm. Moreover, the electronic populations of the full-dimensional on-the-fly calculations are in excellent agreement with the populations of the three-state nine-mode model, which confirms that the internal conversion dynamics of pyrazine is accurately represented by this reduced-dimensional model on the time scale under consideration (200 fs). The original FSSH method, in which the electronic wave function is propagated in the adiabatic representation, yields less accurate results. The oscillations in the populations of the diabatic B 3u (nπ *) and A 1u (nπ *) states driven by the mode Q 8a are also observed in the full-dimensional dynamics simulations.

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Section: Combinations Of Modes Numbers Of Spfs Numbers Of Grid Pointsmentioning

confidence: 99%

mentioning

confidence: 99%

Assessing the performance of trajectory surface hopping methods: Ultrafast internal conversion in pyrazine

Xie

Sapunar

Došlić

et al. 2019

The Journal of Chemical Physics

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“…We close by noting that the ability to rapidly and accurately determine diabatic potentials will be directly applicable to on-the-fly quantum dynamics simulations. In particular, the combination of DFT/MRCI P-BDD calculations and on-the-fly machine learning [50][51][52][53][54] holds promise for the construction of a powerful, near-black box framework for the use of DFT/MRCI in on-the-fly dynamics calculations, and will be the focus of future work in our group.…”

Section: Discussionmentioning

confidence: 99%

Propagative block diagonalization diabatization of DFT/MRCI electronic states

Neville

Seidu

Schuurman

2020

The Journal of Chemical Physics

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We present a framework for the calculation of diabatic states using the combined density functional theory and multireference configuration interaction (DFT/MRCI) method. Due to restrictions present in the current formulation of the DFT/MRCI method (a lack of analytical derivative couplings and the inability to use non-canonical Kohn-Sham orbitals), most common diabatisation strategies are not applicable. We demonstrate, however, that diabatic wavefunctions and potentials can be calculated at the DFT/MRCI level of theory using a propagative variant of the block diagonalisation diabatisation method (P-BDD). The proposed procedure is validated via the calculation of diabatic potentials for LiH and the simulation of the vibronic spectrum of pyrazine. In both cases, the combination of the DFT/MRCI and P-BDD methods is found to correctly recover the non-adiabatic coupling effects of the problem.

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“…Many of them were mainly designed to build the diabatic wavefunctions for molecular systems when the adiabatic wavefunctions are available. 17,[19][20][21][22][23][24][25][39][40][41] Alternatively, it is also possible to build the diabatic states directly by assuming the smooth property constrain of the diabatic electronic wavefunction. 26,[28][29][30][31][32][42][43][44] Although many diabatic methods have been well established, it is still not easy to construct the diabatic Hamiltonian for the large or extended systems, if many-electro n wavefunctions that are the linear combination of the slater determinants are considered .…”

Section: Tocmentioning

confidence: 99%

Diabatic Hamiltonian construction in van der Waals heterostructure complexes

et al. 2019

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A diabatization method is developed for the approximated description of the photoinduced charge separation/transfer processes in the van der Waals (vdW) heterostructure complex, which is based on the wavefunction projection approach using a plane wave basis set in the framework of the single-particle picture. We build the diabatic Hamiltonian for the description of the interlayer photoinduced hole-trans fer process of the two-dimensional vdW MoS2/WS2 heterostructure complexes. The diabatic Hamiltonian gives the energies of the localized valence band states (located at MoS2 and valence band states (located at WS2), as well as the couplings between them.The wavefunction projection method provides a practical and reasonable approach to construct the diabatic model in the description of photoinduced charge transfer processes in the vdW heterostructure complexes.

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Improved on-the-Fly MCTDH Simulations with Many-Body-Potential Tensor Decomposition and Projection Diabatization

Abstract: Please refer to published version for the most recent bibliographic citation information. If a published version is known of, the repository item page linked to above, will contain details on accessing it.

Cited by 39 publications

References 68 publications

Assessing the performance of trajectory surface hopping methods: Ultrafast internal conversion in pyrazine

Assessing the performance of trajectory surface hopping methods: Ultrafast internal conversion in pyrazine

Propagative block diagonalization diabatization of DFT/MRCI electronic states

Diabatic Hamiltonian construction in van der Waals heterostructure complexes

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