A molecular perspective on Tully models for nonadiabatic dynamics

Ibele, Lea M.; Curchod, Basile F. E.

doi:10.1039/d0cp01353f

Cited by 70 publications

(136 citation statements)

References 124 publications

(143 reference statements)

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“…Ethylene dynamics has been extensively investigated with many theoretical approaches, including wavepacket dynamics 60 , on-the-fly quasi-diabatic dynamics 61 , multiple spawning [62][63][64][65] multiconfigurational Ehrenfest 66 , and surface hopping 32,[67][68][69][70][71][72] .…”

Section: A Ethylenementioning

confidence: 99%

“…Fulvene nonadiabatic dynamics has been discussed before based on different simulation approaches, including wavepacket propagation in reduced-dimensionality [75][76][77][78][79] , full-dimensionality direct-surface wavepacket propagation 80,81 , multiple spawning 32 , and surface hopping 32,82 . Fulvene has an extended S 1 /S 0 crossing seam from planar to 90° twisted structures 36,82,83 .…”

Section: B Fulvenementioning

confidence: 99%

“…We tested it by performing decoherence-corrected (DC) FSSH dynamics for ethylene and fulvene (Figure 1) using TD-BA couplings and comparing the results to DC-FSSH dynamics of these molecules using full nonadiabatic coupling vectors. Dynamics of both systems have been extensively studied before, and, recently, Ibele and Curchod 32 proposed that they may be considered molecular examples for two of the three basic 1D Tully models 20 .…”

Section: Introductionmentioning

confidence: 99%

“…Ethylene is a crucial prototype 32 for internal conversion in various systems as diverse as protonated Schiff bases 33 , substituted polyenes 34 , and purine bases 35 . In turn, fulvene poses the challenge of S 1 ↔S 0 recurrences at an extended crossing seam with both peaked and sloped conical intersections 36 .…”

Section: Introductionmentioning

confidence: 99%

“…Ibele et al (ref. 32) proposed three Tully models, i.e., ethylene, fulvene, and DMABN, to benchmark surface hopping methods. Is there any reason why the authors have chosen ethylene and fulvene and did not consider DMABN?…”

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confidence: 99%

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Fewest switches surface hopping with Baeck-An couplings

Casal¹,

Toldo²,

Pinheiro³

et al. 2021

Open Res Europe

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In the Baeck-An (BA) approximation, first-order nonadiabatic coupling vectors are given in terms of adiabatic energy gaps and the second derivative of the gaps with respect to the coupling coordinate. In this paper, a time-dependent (TD) BA approximation is derived, where the couplings are computed from the energy gaps and their second time-derivatives. TD-BA couplings can be directly used in fewest switches surface hopping, enabling nonadiabatic dynamics with any electronic structure methods able to provide excitation energies and energy gradients. Test results of surface hopping with TD-BA couplings for ethylene and fulvene show that the TD-BA approximation delivers a qualitatively correct picture of the dynamics and a semiquantitative agreement with reference data computed with exact couplings. Nevertheless, TD-BA does not perform well in situations conjugating strong couplings and small velocities. Considered the uncertainties in the method, TD-BA couplings could be a competitive approach for inexpensive, exploratory dynamics with a small trajectories ensemble. We also assessed the potential use of TD-BA couplings for surface hopping dynamics with time-dependent density functional theory (TDDFT), but the results are not encouraging due to singlet instabilities near the crossing seam with the ground state.

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Section: A Ethylenementioning

confidence: 99%

Section: B Fulvenementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Fewest switches surface hopping with Baeck-An couplings

Casal¹,

Toldo²,

Pinheiro³

et al. 2021

Open Res Europe

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Automatized protocol and interface to simulate QM/MM time‐resolved transient absorption at TD‐DFT level with COBRAMM

et al. 2022

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We present a series of new implementations that we recently introduced in COBRAMM, the open-source academic software developed in our group. The goal of these implementations is to offer an automatized workflow and interface to simulate time-resolved transient absorption (TA) spectra of medium-to-big chromophore embedded in a complex environment. Therefore, the excited states absorption and the stimulated emission are simulated along nonadiabatic dynamics performed with trajectory surface hopping. The possibility of treating systems from medium to big size is given by the use of time-dependent density functional theory (TD-DFT) and the presence of the environment is taken into account employing a hybrid quantum mechanics/molecular mechanics (QM/MM) scheme. The full implementation includes a series of auxiliary scripts to properly setup the QM/MM system, the calculation of the wavefunction overlap along the dynamics for the propagation, the evaluation of the transition dipole moment at linear response TD-DFT level, and scripts to setup, run and analyze the TA from an ensemble of trajectories. Altogether, we believe that our implementation will open the door to the easily simulate the time-resolved TA of systems so far computationally inaccessible.

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Probing the sensitivity of ab initio multiple spawning to its parameters

Lassmann

Curchod

2023

Theor Chem Acc

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Full multiple spawning (FMS) offers a strategy to simulate the nonadiabatic dynamics of molecular systems by describing their nuclear wavefunctions by a linear combination of coupled trajectory basis functions (TBFs). Applying a series of controlled approximations to the full multiple spawning (FMS) equations leads to the ab initio multiple spawning (AIMS), which is compatible with an on-the-fly propagation of the TBFs and an accurate description of nonadiabatic processes. The AIMS strategy and its numerical implementations, however, rely on a series of user-defined parameters. Herein, we investigate the influence of these parameters on the electronic-state population of two molecular systems— trans-azomethane and a two-dimensional model of the butatriene cation. This work highlights the stability of AIMS with respect to most of its parameters, underlines the specific parameters that require particular attention from the user of the method, and offers prescriptions for an informed selection of their value.

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A molecular perspective on Tully models for nonadiabatic dynamics

Abstract: We present a series of standardized molecular tests for nonadiabatic dynamics, reminiscent of the one-dimensional Tully models proposed in 1990.

Cited by 70 publications

References 124 publications

Fewest switches surface hopping with Baeck-An couplings

Fewest switches surface hopping with Baeck-An couplings

Automatized protocol and interface to simulate QM/MM time‐resolved transient absorption at TD‐DFT level with COBRAMM

Probing the sensitivity of ab initio multiple spawning to its parameters

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