Mechanistic Insights into Electronic Current Flow through Quinone Devices.

Molecular switches based on functionalized graphene nanoribbons (GNRs) are of great interest in the development of nanoelectronics. In experiment, it was found that a significant difference in the conductance of an anthraquinone derivative can be achieved by altering the pH value of the environment. Building on this, in this work we investigate the underlying mechanism behind this effect and propose a general design principle for a pH based GNR-based switch. The electronic structure of the investigated systems is calculated using density functional theory and the transport properties at the quasi-stationary limit are described using nonequilibrium Green's function and the Landauer formalism. This approach enables the examination of the local and the global transport through the system. The electrons are shown to flow along the edges of the GNRs. The central carbonyl groups allow for tunable transport through control of the oxidation state via the pH environment. Finally, we also test different types of GNRs (zigzag vs. armchair) to determine which platform provides the best transport switchability.

A posteriori localization of many-body excited states through simultaneous diagonalization.

In this paper we propose a numerical method to localize many-electron excited states. To characterize the electronic structure of the electronic excited states of a system, quantum chemistry methods typically yield a delocalized description of the excitations. Some a priori localization methods have been developed to provide an intuitive local picture of the excited states. They typically require a good strategy to separate the system of interest from its environment, or a set of a priori localized orbitals, that may reduce their computational accuracy. Here, we introduce an a posteriori method to localize delocalized many-body excited states directly obtained from quantum chemistry calculations. A localization metric for the excited states is defined from their representation as electron-hole pairs, which is encoded in the transition density matrix. This novel a posteriori strategy thus allows to localize excitons within a volume around selected fragments of a complex molecular system without tempering with its quantum chemical treatment. The method is tested on π-stacked oligomers of phenanthrenes and pyrenes. It is found to efficiently localize and separate the excitons according to their character while preserving the information about delocalized many-body states at a low computational cost.

Probing Electronic Symmetry Reduction during Charge Migration via Time-Resolved X-Ray Diffraction.

The present work focuses on probing ultrafast charge migration after symmetry-breaking excitation using ultrashort laser pulses. LiCN is chosen as prototypical system because it can be oriented in the laboratory frame and it possesses optically-accessible charge transfer states at low energies. The charge migration is simulated within the hybrid time-dependent density functional theory/configuration interaction framework. Time-resolved electronic current densities and simulated time-resolved x-ray diffraction signals are used to unravel the mechanism of charge migration. Our simulations demonstrate that specific choices of laser polarization lead to a control over the symmetry of the induced charge migration. Moreover, time-resolved x-ray diffraction signals are shown to encode transient symmetry reduction at intermediate times.

Stochastic multi-configuration time-dependent Hartree for dissipative quantum dynamics with strong intramolecular coupling.

In this article, we explore the dissipation dynamics of a strongly coupled multidimensional system in contact with a Markovian bath, following a system-bath approach. We use in this endeavor the recently developed stochastic multi-configuration time-dependent Hartree approach within the Monte Carlo wave packet formalism [S. Mandal et al., J. Chem. Phys. 156, 094109 (2022)]. The method proved to yield thermalized ensembles of wave packets when intramolecular coupling is weak. To treat strongly coupled systems, new Lindblad dissipative operators are constructed as linear combinations of the system coordinates and associated momenta. These are obtained by a unitary transformation to a normal mode representation, which reduces intermode coupling up to second order. Additionally, we use combinations of generalized raising/lowering operators to enforce the Boltzmann distribution in the dissipation operators, which yield perfect thermalization in the harmonic limit. The two ansatz are tested using a model two-dimensional Hamiltonian, parameterized to disentangle the effects of intramolecular potential coupling, of strong mode mixing observed in Fermi resonances, and of anharmonicity.

Multidimensional stochastic dissipative quantum dynamics using a Lindblad operator.

In this paper, multidimensional dissipative quantum dynamics is studied within a system-bath approach in the Markovian regime using a model Lindblad operator. We report on the implementation of a Monte Carlo wave packet algorithm in the Heidelberg version of the Multi-Configuration Time-Dependent Hartree (MCTDH) program package, which is henceforth extended to treat stochastic dissipative dynamics. The Lindblad operator is represented as a sum of products of one-dimensional operators. The new form of the operator is not restricted to the MCTDH formalism and could be used with other multidimensional quantum dynamical methods. As a benchmark system, a two-dimensional coupled oscillators model representing the internal stretch and the surface-molecule distance in the O2/Pt(111) system coupled to a Markovian bath of electron-hole-pairs is used. The simulations reveal the interplay between coherent intramolecular coupling due to anharmonic terms in the potential and incoherent relaxation due to coupling to an environment. It is found that thermalization of the system can be approximately achieved when the intramolecular coupling is weak.

Theoretical modeling of molecules in weakly interacting environments: trifluoride anions in argon.

The properties of molecules can be affected by the presence of a host environment. Even in inert rare gas matrices such effects are observable, as for instance in matrix isolation spectroscopy. In this work we study the trifluoride anion in cryogenic argon environments. To investigate the structure and vibrational properties of the guest-host systems, a potential energy surface of compound F-3-argon structures is determined from ab initio calculations with the CCSD(T)-F12b approach. Argon environments are probed with minima hopping optimizations of extended trifluoride-argon clusters. The vibrations of F-3 within the optimized environments are examined with anharmonic vibrational analyses. Among the three identified structural surroundings for the trifluoride, two are characterized by relatively favorable guest-host and host-host interactions as well as vibrational zero-point energies. A striking dependence of the trifluoride properties on the particular argon environment reveals the delicate influence of the host atoms on the guest molecule. Very good agreement with measured data suggests that in experiment F-3 occupies a double-vacancy site.

The Peculiar Interaction of Trifluoride Anions with Cryogenic Rare Gas Matrices.

In this contribution, we present theoretical modeling of the interaction between rare gas matrices and a trifluoride guest anion, as well as its quantitative effect on measured vibrational spectra. Using a combination of coupled-cluster electronic structure calculations and a many-body potential expansion coupled with permutation invariant polynomial fitting and anharmonic vibrational spectrum simulations, we shed light on the origin of the trifluoride matrix effects observed experimentally. The theoretical spectra are found to reproduce accurately the measured data while providing deeper insights into the effects of the guest-host interaction. The investigations reveal that neon can only stabilize trifluoride in hexagonal cavities formed by double vacancies, while argon can host the anion in a variety of cavities ranging from zero to two defects in the matrix. The origin of this structural variability can be traced back to the disparate strengths of the host-host interactions in neon and argon. The present work demonstrates the importance of theoretical modeling to complement matrix isolation experiments, which alone do not provide direct information about the structure of the matrices or about the physical origin of their interaction and of their spectroscopic signature.

Ethical Artificial Intelligence in Chemical Research and Development: A Dual Advantage for Sustainability.

Artificial intelligence can be a game changer to address the global challenge of humanity-threatening climate change by fostering sustainable development. Since chemical research and development lay the foundation for innovative products and solutions, this study presents a novel chemical research and development process backed with artificial intelligence and guiding ethical principles to account for both process- and outcome-related sustainability. Particularly in ethically salient contexts, ethical principles have to accompany research and development powered by artificial intelligence to promote social and environmental good and sustainability (beneficence) while preventing any harm (non-maleficence) for all stakeholders (i.e., companies, individuals, society at large) affected.

Laser-Induced Electron Symmetry Restoration in Oriented Molecules Made Simple.

Electron symmetry determines many important properties of molecules, from selection rules for photoelectron spectroscopy to symmetry selection rules for chemical reactions. The original electron symmetry is broken if a laser pulse changes the initial state, typically the ground state g, to a superposition of g and an excited state e with different irreducible representations (IRREPs). Quantum dynamics simulations for two examples, the oriented benzene and LiCN molecules, show that the original electron symmetry can be restored by means of a reoptimized π-laser pulse which transfers the component in the excited state e to another state e', or to several others with the same IRREP as the ground state. This method lends itself to much easier experimental applications than all previous ones because it allows the healing of electron symmetry immediately, without any attosecond constraint on the timing of the second pulse.

Atomistic Simulations of Laser-Controlled Exciton Transfer and Stabilization in Symmetric Double Quantum Dots.

The creation, transfer, and stabilization of localized excitations are studied in a donor-acceptor Frenkel exciton model in an atomistic treatment of reduced-size double quantum dots (QDs) of various sizes. The explicit time-dependent dynamics simulations carried out by hybrid time-dependent density functional theory/configuration interaction show that laser-controlled hole trapping in stacked, coupled germanium/silicon quantum dots can be achieved by a UV/IR pump-dump pulse sequence. The first UV excitation creates an exciton localized on the topmost QD and after some coherent transfer time, an IR pulse dumps and localizes an exciton in the bottom QD. While hole trapping is observed in each excitation step, we show that the stability of the localized electron depends on its multiexcitonic character. We present how size and geometry variations of three Ge/Si nanocrystals influence transfer times and thus the efficiency of laser-driven populations of the electron-hole pair states.

Local current analysis on defective zigzag graphene nanoribbons devices for biosensor material applications.

In this contribution, we aim at investigating the mechanism of biosensing in graphene-based materials from first principles. Inspired by recent experiments, we construct an atomistic model composed of a pyrene molecule serving as a linker fragment, which is used in experiment to attach certain aptamers, and a defective zigzag graphene nanoribbons (ZGNRs). Density functional theory including dispersive interaction is employed to study the energetics of the linker absorption on the defective ZGNRs. Combining non-equilibrium Green's function and the Landauer formalism, the total current-bias voltage dependence through the device is evaluated. Modifying the distance between the linker molecule and the nanojunction plane reveals a quantitative change in the total current-bias voltage dependence, which correlates to the experimental measurements. In order to illuminate the geometric origin of these variation observed in the considered systems, the local currents through the device are investigated using the method originally introduced by Evers and co-workers. In our new implementation, the numerical efficiency is improved by applying sparse matrix storage and spectral filtering techniques, without compromising the resolution of the local currents. Local current density maps qualitatively demonstrate the local variation of the interference between the linker molecule and the nanojunction plane.

Time-resolved imaging of correlation-driven charge migration in light-induced molecular magnets by X-ray scattering.

In this contribution, we investigate the effect of correlation-induced charge migration on the stability of light-induced ring currents, with potential application as molecular magnets. Laser-driven electron dynamics is simulated using density-matrix based time-dependent configuration interaction. The time-dependent many-electron wave packet is used to reconstruct the transient electronic current flux density after excitation of different target states. These reveal ultrafast correlation-driven fluctuations of the charge migration over the molecular scaffold, sometimes leading to large variations of the induced magnetic field. The effect of electron correlation and non-local pure dephasing on the charge migration pattern is further investigated by means of time-resolved X-ray scattering, providing a connection between theoretical predictions of the charge migration mechanism and experimental observables.

A pair potential modeling study of F3- in neon matrices.

In this study, the structural and vibrational properties of a trifluoride anion trapped in solid neon are investigated. For that, a potential energy surface based on a truncated many-body expansion scheme is constructed from explicitly correlated coupled cluster calculations. Cluster modeling and minima hopping optimizations are used to evaluate different neon environments, revealing a dominant underlying structural motif in the guest-host system. Moreover, vibrational analyses of the trapped trifluoride anion are performed. These show the subtle ways in which the neon matrix affects the vibrational properties of the trifluoride. In particular, the vibrational states are slightly compressed and fundamental transitions are blue-shifted within the matrix. Also, the calculated vibrational transition energies are in quantitative agreement with available experimental observations, validating the employed procedure for future applications.

Conformational control over π-conjugated electron pairing in 1D organic polymers.

During the past decades π-conjugated bi-radicals have attracted increasing attention, due to the existence of two close-in-energy resonant electronic configurations with very distinct characteristics: the open-shell bi-radical and the closed-shell quinoidal. The chemical design of the bi-radical structure has been shown to be very effective to shift the balance towards one, or the other, electronic distribution. Some reports have experimentally studied the analogous 1D oligomers and polymers, however, only the open-shell multi-radical configuration has been detected, and it is yet not very clear which structural and chemical parameters are relevant in such extended systems. In this work, via first principles quantum chemical simulations, we study a series of π-conjugated 1D polymers based on triarylmethyl radicals with different chemical functionalization. We find that dihedral angles of the aryl rings connecting the radical centres are the key conformational parameter determining the electronic balance. This provides a simple recipe to use chemical functionalization of aryl rings as a tool to shift the system towards either the electron paired or unpaired configurations. Additionally, we find such conformational control is also effective under the effect of thermal fluctuations, which highlights its potential technological applicability.

Attosecond Charge Migration Can Break Electron Symmetry While Conserving Nuclear Symmetry.

Charge migration moves electrons from one molecular site to another, in a typical time domain from few hundred attoseconds to few femtoseconds. On this timescale, the nuclei stand practically still, implying that the nuclear point group symmetry is conserved. Because electrons move ultrafast, this can lead to a surprising effect, namely, breaking the spatial symmetry of the electron density in spite of the conservation of nuclear framework symmetry. We demonstrate theoretically that attosecond charge migration achieves this electron symmetry breaking if the electrons are prepared in a coherent superposition of nondegenerate electronic ground and excited states which transform according to different irreducible representations. Two simple examples provide a proof-of-principle, namely, periodic attosecond charge migration in the σg + σu superposition state of the aligned H2+ cation (nuclear point group D∞h, but electron symmetry breaking D∞h → C∞v) and in the A1 + B2 superposition state of the oriented H2O molecule (C2v vs C2v → Cs).

Scattering of NO(ν = 3) from Au(111): a stochastic dissipative quantum dynamical perspective.

In this work, we present a theoretical study of the scattering dynamics of NO(ν = 3) from an ideal unreconstructed Au(111) surface. The simulations are performed in reduced dimensions at the three high-symmetry sites employing our recent modification to the stochastic wave packet approach for diatomic-metal scattering [J. Chem. Phys., 2019, 150, 184105]. Energy exchange between molecular vibrational degrees of freedom and the electron-hole pairs (EHP) of the metal is accounted for by quantized stochastic jump operators, with associated rates obtained from a microscopic model based on Fermi's golden rule. The simulations are found to reproduce the experimentally observed trend of enhanced vibrational relaxation probabilities with increasing initial translational energy. Molecular dynamics simulations with electronic friction (MDEF) in the independent atom approximation were performed to compare classical and quantum dynamical descriptions of that system. Significant differences between these two descriptions were found indicating that intermode coupling must be described accurately by using a good potential energy surface, and pointing out at the potentially important influence of a quantized description of energy relaxation in describing the scattering of NO from Au(111).

Probing Electronic Fluxes via Time-Resolved X-Ray Scattering.

The current flux density is a vector field that can be used to describe theoretically how electrons flow in a system out of equilibrium. In this work, we unequivocally demonstrate that the signal obtained from time-resolved x-ray scattering does not only map the time evolution of the electronic charge distribution, but also encodes information about the associated electronic current flux density. We show how the electronic current flux density qualitatively maps the distribution of electronic momenta and reveals the underlying mechanism of ultrafast charge migration processes, while also providing quantitative information about the timescales of electronic coherences.

Tuning PtII -Based Donor-Acceptor Systems through Ligand Design: Effects on Frontier Orbitals, Redox Potentials, UV/Vis/NIR Absorptions, Electrochromism, and Photocatalysis.

Asymmetric platinum donor-acceptor complexes [(pimp)Pt(Q2- )] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q2- =catecholate-type donor ligands. The properties of the complexes are evaluated as a function of the donor ligands, and correlations are drawn among electrochemical, optical, and theoretical data. Special focus has been put on the spectroelectrochemical investigation of the complexes featuring sulfonyl-substituted phenylendiamide ligands, which show redox-induced linkage isomerism upon oxidation. Time-dependent density functional theory (TD-DFT) as well as electron flux density analysis have been employed to rationalize the optical spectra of the complexes and their reactivity. Compound 1 ([(pimp)Pt(Q2- )] with Q2- =3,5-di-tert-butylcatecholate) was shown to be an efficient photosensitizer for molecular oxygen and was subsequently employed in photochemical cross-dehydrogenative coupling (CDC) reactions. The results thus display new avenues for donor-acceptor systems, including their role as photocatalysts for organic transformations, and the possibility to introduce redox-induced linkage isomerism in these compounds through the use of sulfonamide substituents on the donor ligands.