NMR Coupling Constants Based on the Bethe–Salpeter Equation in the <i>GW</i> Approximation

Franzke, Yannick J.; Holzer, Christof; Mack, Fabian

doi:10.1021/acs.jctc.1c00999

Cited by 34 publications

(47 citation statements)

References 177 publications

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“…For completeness, we also note that in principle our method is not limited to TD-DFT, but can also be used within the Greens function based GW-Bethe-Salpeter equation framework. [36,37]…”

Section: Dft Implementationmentioning

confidence: 99%

A Multi‐Scale Approach for Modeling the Optical Response of Molecular Materials Inside Cavities

et al. 2022

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The recent fabrication advances in nanoscience and molecular materials point toward a new era where material properties are tailored in silico for target applications. To fully realize this potential, accurate and computationally efficient theoretical models are needed for: a) the computer‐aided design and optimization of new materials before their fabrication; and b) the accurate interpretation of experiments. The development of such theoretical models is a challenging multi‐disciplinary problem where physics, chemistry, and material science are intertwined across spatial scales ranging from the molecular to the device level, that is, from ångströms to millimeters. In photonic applications, molecular materials are often placed inside optical cavities. Together with the sought‐after enhancement of light‐molecule interactions, the cavities bring additional complexity to the modeling of such devices. Here, a multi‐scale approach that, starting from ab initio quantum mechanical molecular simulations, can compute the electromagnetic response of macroscopic devices such as cavities containing molecular materials is presented. Molecular time‐dependent density‐functional theory calculations are combined with the efficient transition matrix based solution of Maxwell's equations. Some of the capabilities of the approach are demonstrated by simulating surface metal‐organic frameworks ‐in‐cavity and J‐aggregates‐in‐cavity systems that have been recently investigated experimentally, and providing a refined understanding of the experimental results.

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“…For completeness, we also note that in principle our method is not limited to TD-DFT, but can also be used within the Greens function based GW-Bethe-Salpeter equation framework. [36,37]…”

Section: Dft Implementationmentioning

confidence: 99%

A Multi‐Scale Approach for Modeling the Optical Response of Molecular Materials Inside Cavities

et al. 2022

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“…Also, while outlined for TD-DFT in this work, recent developments have shown that also the GW –Bethe–Salpeter equation method can be applied to solve eq 1 . 31 , 34 …”

Section: Methodsmentioning

confidence: 99%

Multiscale Modeling of Broadband Perfect Absorbers Based on Gold Metallic Molecules

2022

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The modeling of functional photonic devices that rely on molecular materials continues to be a major contemporary challenge. It is a challenge because, in the Maxwell equations, which govern the light-matter interaction, material properties are primarily introduced on phenomenological grounds and not from first principles. To overcome such limitations, we outline a multiscale modeling approach that bridges multiple length scales. We can predict with our approach the optical response of a photonic device that exploits in its design molecular materials whose properties were determined using time-dependent density functional theory. The specifically considered device is a broadband perfect absorber that uses in part a thin film comprising gold molecules made from 144 atoms. Our methodology discloses various chemical and physical effects that define such a device’s response. Our methodology is versatile, and a larger number of applications will profit from this development.

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“…91,92 Additionally, geometry gradients are implemented for meta-GGAs by extension of the existing machinery. 26,112 Furthermore, CDFT is available for the XC kernel of excitation energies from time-dependent density functional theory 95 (TD-DFT) and the contracted Bethe-Salpeter equation (cBSE), 113 NMR spinspin coupling constants, 74,75 as well as static, dynamic, and damped polarizabilities. 28 Additionally, the XC kernel is the only relevant DFT ingredient for NMR shieldings and shifts with a common gauge origin.…”

Section: Methodsmentioning

confidence: 99%

“…In this work, CDFT will therefore be applied to the self-consistent treatment of spin-orbit interaction and we study its impact on ground-state energies, excitation energies and magnetic resonance parameters. Besides calculations in strong magnetic fields and CDFT, the generalized kinetic energy density was applied to linear response theory for time-dependent density functional theory (TD-DFT), 68,69 electron paramagnetic resonance (EPR) spectra, 70,71 nuclear magnetic resonance (NMR) properties, [70][71][72][73][74][75] and magnetizabilities. 73 In all these approaches, the paramagnetic current density of the ground state was assumed to vanish.…”

Section: Introductionmentioning

confidence: 99%

Current density functional framework for spin–orbit coupling

Holzer

Franzke

Pausch

2022

Preprint

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Relativistic two-component and four-component density functional calculations are carried out in a non-collinear formalism to describe spin-orbit interaction. The exchange-correlation functional itself is constructed as a straightforward generalization of the non-relativistic density functional approximation. However, spin-orbit coupling is a form of magnetic induction and generally leads to a non-vanishing paramagnetic current density. This means that functionals depending on the kinetic energy density such as meta-generalized gradient approximations and local hybrid functionals should be constructed in the framework of current density functional theory (CDFT), which is (almost) exclusively used in the regime of strong magnetic fields. Herein, we present a CDFT approach for spin-orbit coupling, which leads to current-dependent terms in the potential and its derivatives. The ansatz is implemented for the exchange-correlation potential and the exchange-correlation kernel, making it applicable to a wide range of molecular properties. We assess the importance of the current density terms for ground-state energies, excitation energies, nuclear magnetic resonance (NMR) shielding and spin-spin coupling constants, as well as hyperfine coupling constants and ∆g-shifts in electron paramagnetic resonance (EPR) spectroscopy. The most notable changes are found for EPR properties. The impact of the current-dependent terms rises with the number of unpaired electrons and consequently EPR properties are more sensitive towards CDFT. Considerable changes in the results are observed for the strongly constrained and appropriately normed (SCAN) functionals, as well as the B97M family and TASK. The current density terms are less important when exact exchange is incorporated. Consequently, the results with (local) hybrid functionals are not substantially affected. At the same time, the current density does not notably increase the computational costs for hybrid functionals, but the current-dependent kernel ensures the stability of response calculations in all cases. We therefore strongly recommend to use the framework of CDFT for self-consistent spin-orbit calculations.

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NMR Coupling Constants Based on the Bethe–Salpeter Equation in the GW Approximation

Cited by 34 publications

References 177 publications

A Multi‐Scale Approach for Modeling the Optical Response of Molecular Materials Inside Cavities

A Multi‐Scale Approach for Modeling the Optical Response of Molecular Materials Inside Cavities

Multiscale Modeling of Broadband Perfect Absorbers Based on Gold Metallic Molecules

Current density functional framework for spin–orbit coupling

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