Cavity-modulated ionization potentials and electron affinities from quantum electrodynamics coupled-cluster theory
TL;DR: Ionization potentials and electron affinities are presented, and it is demonstrated that EAs are easily modulated by cavity interactions, while IPs for these compounds are far less sensitive to the presence of the cavity.
Abstract: Quantum electrodynamics coupled-cluster (QED-CC) theory is used to model vacuum-field-induced changes to ground-state properties of a series of sodium halide compounds (NaX, X = F, Cl, Br, I) strongly coupled to an optical cavity. Ionization potentials (IPs) and electron affinities (EAs) are presented, and it is demonstrated that EAs are easily modulated by cavity interactions, while IPs for these compounds are far less sensitive to the presence of the cavity. EAs predicted by QED-CC can be reduced by as much 0.22 eV (or ~50%) when considering experimentally-accessible coupling parameters.
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TL;DR: It is demonstrated that electron-photon correlation is fundamental to describe intermolecular interactions in strong light-matter coupling and proposed optical cavities as a novel tool to manipulate and control ground state properties, solvent effects, and intermolescular interactions for molecules and materials.
Abstract: Intermolecular bonds are weak compared to covalent bonds, but they are strong enough to influence the properties of large molecular systems. In this work, we investigate how strong light-matter coupling inside an optical cavity can modify these intermolecular forces. We perform a detailed comparison between currently available ab initio electron-photon methodologies. The electromagnetic field inside the cavity can modulate the ground state properties of weakly bound complexes. Controlling the field polarization, the interactions can be stabilized or destabilized, and electron densities, dipole moments, and polarizabilities can be altered. We demonstrate that electron-photon correlation is fundamental to describe intermolecular interactions in strong light-matter coupling. This work proposes optical cavities as a novel tool to manipulate and control ground state properties, solvent effects, and intermolecular interactions for molecules and materials.
47 citations
TL;DR: In this article , the authors present a survey of the state of the art in bioinformatics and biomedicine research, including the following papers: http://www.firstpage
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TL;DR: In this article , the QED-CC-in-QED-SCF projection-based embedding method inherits all the favorable properties from the two worlds: computational efficiency and accuracy.
Abstract: Polaritonic chemistry relies on the strong light-matter interaction phenomena for altering the chemical reaction rates inside optical cavities. To explain and understand these processes, the development of reliable theoretical models is essential. While computationally efficient quantum electrodynamics self-consistent field (QED-SCF) methods, such as quantum electrodynamics density functional theory, need accurate functionals, quantum electrodynamics coupled cluster (QED-CC) methods provide a systematic increase in accuracy but at much greater cost. To overcome this computational bottleneck, herein we introduce and develop the QED-CC-in-QED-SCF projection-based embedding method that inherits all the favorable properties from the two worlds: computational efficiency and accuracy. The performance of the embedding method is assessed by studying some prototypical but relevant reactions, such as methyl transfer reaction, proton transfer reaction, and protonation reaction, in a complex environment. The results obtained with the new embedding method are in excellent agreement with more expensive QED-CC results. The analysis performed on these reactions indicates that the electron-photon correlation effects are local in nature and that only a small region should be treated at the QED-CC level for capturing important effects due to cavity. This work sets the stage for future developments of polaritonic quantum chemistry methods and will serve as a guideline for the development of other polaritonic embedding models.
14 citations
Peer Review•
08 Nov 2022
TL;DR: In this paper , the theoretical foundations and first principles frameworks to describe quantum matter within quantum electrodynamics (QED) in the low-energy regime, with a specific focus on polaritonic chemistry, are presented.
Abstract: In this review we present the theoretical foundations and first principles frameworks to describe quantum matter within quantum electrodynamics (QED) in the low-energy regime, with a specific focus on polaritonic chemistry. Having a rigorous and fully quantized description of interacting photons, electrons and nuclei/ions, from weak to strong light-matter coupling regimes, is pivotal for a detailed theoretical understanding of the emerging fields of polaritonic chemistry and cavity materials engineering. At the same time, the use of rigorous first principles avoids ambiguities and problems stemming from using approximate models based on phenomenological descriptions of light, matter and their interactions, and provides a way to systematically derive consistent low-energy models that are fully gauge invariant and mimic the first principles results. By starting from fundamental physical and mathematical principles, we first review in great detail non-relativistic QED, which allows to study polaritonic systems non-perturbatively by solving a Schrödingertype equation. The resulting Pauli-Fierz quantum field theory serves as a cornerstone for the development of (in principle exact but in practice) approximate computational methods, such as quantum-electrodynamical density functional theory, QED coupled cluster or cavity Born-Oppenheimer molecular dynamics. These methods do not depend on phenomenological models of chemical systems, but instead they treat light and matter on equal footing. At the same time, first principles QED methods have the same level of accuracy and reliability as established methods of computational chemistry and electronic structure theory. After an overview of the key-ideas behind those novel ab initio QED methods, we explain their benefits for a better understanding of photoninduced changes of chemical properties and reactions. Based on results obtained by ab initio QED methods we identify the open theoretical questions and how a so far missing mechanistic understanding of polaritonic chemistry can be established. We finally give an outlook on future directions within polaritonic chemistry and first principles QED and address the open questions that need to be solved in the next years both from a theoretical as well as experimental
12 citations
TL;DR: In this article , the residual interaction between an outgoing free electron and the vacuum field is shown to be significant and the free electron-field interaction has sizable effects on the ionization potential of typical organic molecules.
Abstract: The ionization of molecular systems is important in many chemical processes, such as electron transfer and hot electron injection. Strong coupling between molecules and quantized fields (e.g., inside optical cavities) represents a new promising way to modify molecular properties in a non-invasive way. Recently, strong light-matter coupling has shown the potential to significantly improve the rates of hot electron driven processes, for instance, in water splitting. In this paper, we demonstrate that inside an optical cavity, the residual interaction between an outgoing free electron and the vacuum field is significant. We further show that since the quantized field is also interacting with the ionized molecule, the free electron and the molecular system are correlated. We develop a theoretical framework to account for the field induced correlation and show that the interaction between the free electron and the field, free electron-field interaction, has sizable effects on the ionization potential of typical organic molecules.
11 citations
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TL;DR: In this article, a method for the calculation of the matrix elements of the logarithm of an operator which gives the exact wavefunction when operating on the wavefunction in the one-electron approximation is proposed.
Abstract: A method is suggested for the calculation of the matrix elements of the logarithm of an operator which gives the exact wavefunction when operating on the wavefunction in the one‐electron approximation. The method is based on the use of the creation and annihilation operators, hole—particle formalism, Wick's theorem, and the technique of Feynman‐like diagrams. The connection of this method with the configuration‐interaction method as well as with the perturbation theory in the quantum‐field theoretical form is discussed. The method is applied to the simple models of nitrogen and benzene molecules. The results are compared with those obtained with the configuration‐interaction method considering all possible configurations within the chosen basis of one‐electron functions.
2,676 citations
TL;DR: In this article, the essential aspects of coupled-cluster theory are explained and illustrated with informative numerical results, showing that the theory offers the most accurate results among the practical ab initio electronic-structure theories applicable to moderate-sized molecules.
Abstract: Today, coupled-cluster theory offers the most accurate results among the practical ab initio electronic-structure theories applicable to moderate-sized molecules. Though it was originally proposed for problems in physics, it has seen its greatest development in chemistry, enabling an extensive range of applications to molecular structure, excited states, properties, and all kinds of spectroscopy. In this review, the essential aspects of the theory are explained and illustrated with informative numerical results.
2,667 citations
TL;DR: This work characterized and understood the delocalization error and static correlation error of commonly used approximations of density functional theory through the perspective of fractional charges and fractional spins introduced recently.
Abstract: Density functional theory of electronic structure is widely and successfully applied in simulations throughout engineering and sciences. However, for many predicted properties, there are spectacular failures that can be traced to the delocalization error and static correlation error of commonly used approximations. These errors can be characterized and understood through the perspective of fractional charges and fractional spins introduced recently. Reducing these errors will open new frontiers for applications of density functional theory.
2,122 citations
TL;DR: Statistical analysis of vibrational spectroscopy time series and dark-field scattering spectra provides evidence of single-molecule strong coupling, opening up the exploration of complex natural processes such as photosynthesis and the possibility of manipulating chemical bonds.
Abstract: Photon emitters placed in an optical cavity experience an environment that changes how they are coupled to the surrounding light field. In the weak-coupling regime, the extraction of light from the emitter is enhanced. But more profound effects emerge when single-emitter strong coupling occurs: mixed states are produced that are part light, part matter1, 2, forming building blocks for quantum information systems and for ultralow-power switches and lasers. Such cavity quantum electrodynamics has until now been the preserve of low temperatures and complicated fabrication methods, compromising its use. Here, by scaling the cavity volume to less than 40 cubic nanometres and using host–guest chemistry to align one to ten protectively isolated methylene-blue molecules, we reach the strong-coupling regime at room temperature and in ambient conditions. Dispersion curves from more than 50 such plasmonic nanocavities display characteristic light–matter mixing, with Rabi frequencies of 300 millielectronvolts for ten methylene-blue molecules, decreasing to 90 millielectronvolts for single molecules—matching quantitative models. Statistical analysis of vibrational spectroscopy time series and dark-field scattering spectra provides evidence of single-molecule strong coupling. This dressing of molecules with light can modify photochemistry, opening up the exploration of complex natural processes such as photosynthesis and the possibility of manipulating chemical bonds.
1,367 citations
TL;DR: In this article, an approximate Xα functional is proposed from which the charge density fitting equations follow variationally, and the method independent of the fitting (auxiliary) bases to within 0.02 eV.
Abstract: An approximate Xα functional is proposed from which the charge density fitting equations follow variationally. LCAO Xα calculations on atomic nickel and diatomic hydrogen show the method independent of the fitting (auxiliary) bases to within 0.02 eV. Variational properties associated with both orbital and auxiliary basis set incompleteness are used to approach within 0.2 eV the Xα total energy limit for the nitrogen molecule.
1,248 citations