Non-adiabatic approximations in time-dependent density functional theory: progress and prospects

Lacombe, Lionel; Maitra, Neepa T.

doi:10.1038/s41524-023-01061-0

Cited by 12 publications

(9 citation statements)

References 238 publications

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“…Some time ago, the application of a simple time-dependent correlation potential model originally developed for laser-atom interactions [78] showed effects in the antiproton-helium system; however, this did not lead to improvements compared to the IEM, and was dismissed as unsuitable for the collision problem [79]. Progress has been made regarding understanding the properties of the exact TDKS potential, and, as a consequence, of time-dependent correlation effects on a formal level and for model problems (see, e.g., [80,81] and references therein). One lesson learned from these studies concerns the memory dependence of the exact TDKS potential, i.e., a dependence of the potential at time t on the density at times t ′ < t (and the initial state).…”

Section: Discussionmentioning

confidence: 99%

Time-Dependent Density Functional Theory for Atomic Collisions: A Progress Report

Kirchner

2024

Atoms

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In this paper, the current status of time-dependent density functional theory (TDDFT)-based calculations for ion–atom collision problems is reviewed. Most if not all reported calculations rely on the semiclassical approximation of heavy particle collision physics and the time-dependent Kohn–Sham (TDKS) scheme for computing the electronic density of the system. According to the foundational Runge–Gross theorem, all information available about the electronic many-body system is encoded in the density; however, in practice it is often not known how to extract it without resorting to modelling and approximations. This is in addition to a necessarily approximate implementation of the TDKS scheme due to the lack of precise knowledge about the potential that drives the equations. Notwithstanding these limitations, an impressive body of work has been accumulated over the past few decades. A sample of the results obtained for various collision systems is discussed here, in addition to the formal underpinnings and theoretical and practical challenges of the application of TDDFT to atomic collision problems, which are expounded in mostly nontechnical terms. Open problems and potential future directions are outlined as well.

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Section: Discussionmentioning

confidence: 99%

Time-Dependent Density Functional Theory for Atomic Collisions: A Progress Report

Kirchner

2024

Atoms

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“…Time-dependent density functional theory (TD-DFT) is an approach that includes the time domain in the DFT calculations by evaluating the evolution of the electron density of a system that is subjected to a time-dependent external potential . This method can be employed to understand the nature, properties, and chemistry of excited state species in environmentally relevant applications such as molecular sensors and elucidate photoinduced pollutant degradation mechanisms. − TD-DFT calculations can simulate the differential UV-visible absorbance spectra (DAS) of metal–natural organic matter complexes modeled using esculetin complexes. , For instance, esculetin complexes with metal ions with small ionic radii and low electronegativities (e.g., Zn(II), Mg(II), and Ca(II)) result in low calculated DAS intensities, whereas the opposite occurs with larger ions with higher electronegativities (e.g., Pb(II), Cu(II), Al(III), Fe(III), and Cr(III)).…”

Section: Computational Chemistry Methodsmentioning

confidence: 99%

“…154,155 Time-dependent density functional theory (TD-DFT) is an approach that includes the time domain in the DFT calculations by evaluating the evolution of the electron density of a system that is subjected to a time-dependent external potential. 156 This method can be employed to understand the nature, properties, and chemistry of excited state species in environmentally relevant applications such as molecular sensors and elucidate photoinduced pollutant degradation mechanisms. 157−161 TD-DFT calculations can simulate the differential UV-visible absorbance spectra (DAS) of metal− natural organic matter complexes modeled using esculetin complexes.…”

Section: Applications Of Quantum Mechanicsmentioning

confidence: 99%

Computational Chemistry as Applied in Environmental Research: Opportunities and Challenges

Sandoval-Pauker,

Yin,

Castillo

et al. 2023

ACS EST Eng.

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The constant development of computer systems and infrastructure has allowed computational chemistry to become an important component of environmental chemistry research. In the past decade, the application of quantum and classical mechanical calculations to model and understand environmental systems has increased exponentially. In this review, we highlight various applications of computational chemistry techniques in areas of environmental chemistry research (e.g., wastewater/air treatment, sensing, biodegradation). We briefly describe each computational approach, starting with quantum chemistry principle methods followed by molecular mechanics (MM), molecular dynamics (MD), and hybrid QM/MM methods. The recent introduction of artificial intelligence and machine learning techniques and their potential to disrupt the field are also discussed. Challenges and current and future directions to address them are presented.

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“…One of the standard and computationally affordable methods for computing neutral excitations and excited‐state properties in molecules and extended systems is the linear‐response time‐dependent DFT (TD‐DFT) 15–18 . In linear response TD‐DFT, single excitations are explicitly encoded in the KS density‐density response function, from which any true interacting excitation energy (not only single excitation ones) can in principle be retrieved via the frequency‐dependent Hartree‐exchange‐correlation (Hxc) kernel, which relates to the functional derivative of the time‐dependent density‐functional Hxc potential.…”

Section: Introductionmentioning

confidence: 99%

Extended N‐centered ensemble density functional theory of double electronic excitations

Cernatic,

Fromager

2024

J Comput Chem

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A recent work (arXiv:2401.04685) has merged N‐centered ensembles of neutral and charged electronic ground states with ensembles of neutral ground and excited states, thus providing a general and in‐principle exact (so‐called extended N‐centered) ensemble density functional theory of neutral and charged electronic excitations. This formalism made it possible to revisit the concept of density‐functional derivative discontinuity, in the particular case of single excitations from the highest occupied Kohn–Sham (KS) molecular orbital, without invoking the usual “asymptotic behavior of the density” argument. In this work, we address a broader class of excitations, with a particular focus on double excitations. An exact implementation of the theory is presented for the two‐electron Hubbard dimer model. A thorough comparison of the true physical ground‐ and excited‐state electronic structures with that of the fictitious ensemble density‐functional KS system is also presented. Depending on the choice of the density‐functional ensemble as well as the asymmetry of the dimer and the correlation strength, an inversion of states can be observed. In some other cases, the strong mixture of KS states within the true physical system makes the assignment “single excitation” or “double excitation” irrelevant.

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Non-adiabatic approximations in time-dependent density functional theory: progress and prospects

Cited by 12 publications

References 238 publications

Time-Dependent Density Functional Theory for Atomic Collisions: A Progress Report

Time-Dependent Density Functional Theory for Atomic Collisions: A Progress Report

Computational Chemistry as Applied in Environmental Research: Opportunities and Challenges

Extended N‐centered ensemble density functional theory of double electronic excitations

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