Nonadiabatic Coupling in Trajectory Surface Hopping: Accurate Time Derivative Couplings by the Curvature-Driven Approximation

Zhao, Xiaorui; Merritt, Isabella C. D.; Lei, Ruiqing; Shu, Yinan; Jacquemin, Denis; Zhang, Linyao; Xu, Xuefei; Vacher, Morgane; Truhlar, Donald G.

doi:10.1021/acs.jctc.3c00813

Cited by 10 publications

(11 citation statements)

References 74 publications

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“…Time-dependent DFT methods have been discussed [93][94][95]114,115]. The latter approaches to ferrocene have been applied, as well [116].…”

Section: Methodsmentioning

confidence: 99%

Stochastic dynamics mass spectrometric determination of ferrocenes

Ivanova

2024

Preprint

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The paper treats stochastic dynamics mass spectrometric formulas of exact data-processing of measurands; thus, answering a question: How can be inferred reliably analyte identification and annotation from mass spectrometric measurands when omics-methods produce comparable performances among structurally similar analytes? Omics-methods are treated in context of instrumental measurements and data-processing. Exact quantitative and multi-dimensional structural mass spectrometric-based methods for metabolomics contributes crucially to understand biochemical mechanisms, because of metabolites are downstream biochemical products in living systems. Reliable metabolomics provides in-depth knowledge of response within biological fluids and tissues depending on internal and external agents, which is crucial for real time monitoring of human diseases. The study deals with structural analysis of ferroquine and its metabolites in human hepatic models utilizing ultra-high accuracy mass spectrometry, static and molecular dynamics quantum chemical approaches, and chemometrics. It provides excellent-to-exact performances in examining standard organometallics ferrocene and [FeII(L)(CO)2(CH3CN)] (L = 2-(5-oxo-4,6-bis-trimethylsilanyl-3,5-dihydro-1H-cyclopenta[c]pyrrol-2-yl)-ethanesulfonic acid) (|r|=0.99992.) The analysis of ferroquine and its metabolites show |r|=0.99815–0.90814.

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“…Time-dependent DFT methods have been discussed [93][94][95]114,115]. The latter approaches to ferrocene have been applied, as well [116].…”

Section: Methodsmentioning

confidence: 99%

Stochastic dynamics mass spectrometric determination of ferrocenes

Ivanova

2024

Preprint

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“…Both xxMD datasets are structured via a temporal split method, partitioning training and testing data based on trajectory timesteps. We want to emphasize that xxMD datasets do not involve nonadiabatic coupling vectors (NACs) for two reasons: first, the advances in the field of nonadiabatic dynamics have enabled NAC-free nonadiabatic dynamics simulations, for example, curvature-driven dynamics 20 – 24 . Second, the purpose of the current work is to provide a database which includes a wide nuclear configuration space for which the energies and gradients of multiple electronic states are available.…”

Section: Methodsmentioning

confidence: 99%

Beyond MD17: the reactive xxMD dataset

Pengmei,

Liu,

Shu

2024

Sci Data

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System specific neural force fields (NFFs) have gained popularity in computational chemistry. One of the most popular datasets as a bencharmk to develop NFF models is the MD17 dataset and its subsequent extension. These datasets comprise geometries from the equilibrium region of the ground electronic state potential energy surface, sampled from direct adiabatic dynamics. However, many chemical reactions involve significant molecular geometrical deformations, for example, bond breaking. Therefore, MD17 is inadequate to represent a chemical reaction. To address this limitation in MD17, we introduce a new dataset, called Extended Excited-state Molecular Dynamics (xxMD) dataset. The xxMD dataset involves geometries sampled from direct nonadiabatic dynamics, and the energies are computed at both multireference wavefunction theory and density functional theory. We show that the xxMD dataset involves diverse geometries which represent chemical reactions. Assessment of NFF models on xxMD dataset reveals significantly higher predictive errors than those reported for MD17 and its variants. This work underscores the challenges faced in crafting a generalizable NFF model with extrapolation capability.

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“…A recent survey of six photochemical reactions compared results between κFS-TSH-EDC and FS-TSH-EDC. , (Notice that the apparently inaccurate curvature-driven dynamics results in ref were due to a programming error–not to deficiencies in the method; this was corrected in ref .) Table summarizes the final ground-state and excited-state populations at the end of the simulation for κFS-TSH-EDC and FS-TSH-EDC.…”

Section: Examples Of Successful Applicationsmentioning

confidence: 99%

“…Employing overlap integrals to approximate TDCs is preferable to using eq because it alleviates the trivial crossing problem. − The simplest approximation to the TDC from an overlap integral is the Hammes-Schiffer–Tully scheme: T I J MCH true( t + 1 2 normalΔ t true) = S I J MCH false( t , t + normalΔ t false) − S J I MCH false( t , t + normalΔ t false) 2 Δ t More accurate schemes are also available, for example, the norm-preserving interpolation scheme of Meek and Levine . We refer the interested reader to ref for a summary of available schemes.…”

Section: Introduction To Nonadiabatic Dynamics Without Wave Functionsmentioning

confidence: 99%

Generalized Semiclassical Ehrenfest Method: A Route to Wave Function-Free Photochemistry and Nonadiabatic Dynamics with Only Potential Energies and Gradients

Shu,

Truhlar

2024

J. Chem. Theory Comput.

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We reconsider recent methods by which direct dynamics calculations of electronically nonadiabatic processes can be carried out while requiring only adiabatic potential energies and their gradients. We show that these methods can be understood in terms of a new generalization of the well-known semiclassical Ehrenfest method. This is convenient because it eliminates the need to evaluate electronic wave functions and their matrix elements along the mixed quantum-classical trajectories. The new approximations and procedures enabling this advance are the curvature-driven approximation to the time-derivative coupling, the generalized semiclassical Ehrenfest method, and a new gradient correction scheme called the time-derivative matrix (TDM) scheme. When spin–orbit coupling is present, one can carry out dynamics calculations in the fully adiabatic basis using potential energies and gradients calculated without spin–orbit coupling plus the spin–orbit coupling matrix elements. Even when spin–orbit coupling is neglected, the method is useful because it allows calculations by electronic structure methods for which nonadiabatic coupling vectors are unavailable. In order to place the new considerations in context, the article starts out with a review of background material on trajectory surface hopping, the semiclassical Ehrenfest scheme, and methods for incorporating decoherence. We consider both internal conversion and intersystem crossing. We also review several examples from our group of successful applications of the curvature-driven approximation.

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Nonadiabatic Coupling in Trajectory Surface Hopping: Accurate Time Derivative Couplings by the Curvature-Driven Approximation

Cited by 10 publications

References 74 publications

Stochastic dynamics mass spectrometric determination of ferrocenes

Stochastic dynamics mass spectrometric determination of ferrocenes

Beyond MD17: the reactive xxMD dataset

Generalized Semiclassical Ehrenfest Method: A Route to Wave Function-Free Photochemistry and Nonadiabatic Dynamics with Only Potential Energies and Gradients

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