Predominant Binding Mode of Palmatine to DNA.

Palmatine is a protoberberine alkaloid, which may produce singlet oxygen under visible light irradiation and binds to DNA. The fact that singlet oxygen activation in palmatine may be triggered by environmental conditions, and in particular its interaction with nucleic acids, makes it a most suitable candidate for photodynamic therapy and DNA-targeted noninvasive anticancer strategies. Despite these remarkable properties, the actual binding mode between palmatine and DNA has not been resolved, yet.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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 , to a superposition of and an excited state 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 to another state ', or to several others with the same IRREP as the ground state.

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.

A pair potential modeling study of F 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.

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.

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.

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 Pt -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(Q )] are presented in this work, in which pimp=[(2,4,6-trimethylphenylimino)methyl]pyridine and Q =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.

Imaging Time-Dependent Electronic Currents through a Graphene-Based Nanojunction.

To assist the design of efficient molecular junctions, a precise understanding of the charge transport mechanisms through nanoscaled devices is of prime importance. In the present contribution, we present time- and space-resolved electron transport simulations through a nanojunction under time-dependent potential biases. We use the driven Liouville-von Neumann approach to simulate the time evolution of the one-electron density matrix under nonequilibrium conditions, which allows us to capture the ultrafast scattering dynamics, the electronic relaxation process, and the quasi-stationary current limit from the same simulation.

Attosecond Control of Restoration of Electronic Structure Symmetry.

Laser pulses can break the electronic structure symmetry of atoms and molecules by preparing a superposition of states with different irreducible representations. Here, we discover the reverse process, symmetry restoration, by means of two circularly polarized laser pulses. The laser pulse for symmetry restoration is designed as a copy of the pulse for symmetry breaking.

Dipole-Induced Transition Orbitals: A Novel Tool for Investigating Optical Transitions in Extended Systems.

Optical absorption spectra for nanostructures and solids can be obtained from the macroscopic dielectric function within the random phase approximation. While experimental spectra can be reproduced with good accuracy, important properties, such as the charge-transfer character associated with a particular transition, are not retrievable. This contribution presents a computationally inexpensive method for the analysis of optical and excitonic properties for extended systems based on solely their electronic ground-state structure.

Influence of Mesoionic Carbenes on Electro- and Photoactive Ru and Os Complexes: A Combined (Spectro-)Electrochemical, Photochemical, and Computational Study.

In recent years, mesoionic carbenes (MICs) are finding increasing use as building blocks of electro- and photoactive metal complexes. We present here a series of Ru and Os polypyridine complexes where one or two pyridyl moieties of the well-known tris(bipyridine) analogues are replaced by MICs. We probe the structural, electrochemical, UV-vis-NIR/electron paramagnetic resonance spectroelectrochemical, and photophysical properties of these complexes as a function of the number of MICs in them.