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Spectroscopy simulations are of paramount importance for the interpretation of experimental electronic spectra, the disentangling of overlapping spectral features, and the tracing of the microscopic origin of the observed signals. Linear and nonlinear simulations are based on the results drawn from electronic structure calculations that provide the necessary parameterization of the molecular systems probed by light. Here, we investigate the applicability of excited-state properties obtained from linear-response time-dependent density functional theory (TDDFT) in the description of nonlinear spectra by employing the pseudowavefunction approach and compare them with benchmarks from highly accurate RASSCF/RASPT2 calculations and with high temporal resolution experimental results. As a test case, we consider the prediction of femtosecond transient absorption and two-dimensional electronic spectroscopy of a perylene bisimide dye in solution. We find that experimental signals are well reproduced by both theoretical approaches, showing that the computationally cheaper TDDFT can be a suitable option for the simulation of nonlinear spectroscopy of molecular systems that are too large to be treated with higher-level RASSCF/RASPT2 methods.

We demonstrate how optical cavities can be exploited to control both valence- and core-excitations in a prototypical model transition metal complex, ferricyanide ([Fe(iii)(CN)6]3-), in an aqueous environment. The spectroscopic signatures of hybrid light-matter polariton states are revealed in UV/Vis and X-ray absorption, and stimulated X-ray Raman signals. In an UV/Vis cavity, the absorption spectrum exhibits the single-polariton states arising from the cavity photon mode coupling to both resonant and off-resonant valence-excited states. We further show that nonlinear stimulated X-ray Raman signals can selectively probe the bipolariton states via cavity-modified Fe core-excited states. This unveils the correlation between valence polaritons and dressed core-excitations. In an X-ray cavity, core-polaritons are generated and their correlations with the bare valence-excitations appear in the linear and nonlinear X-ray spectra.

The Chronus Quantum (ChronusQ) software package is an open source (under the GNU General Public License v2) software infrastructure which targets the solution of challenging problems that arise in ab initio electronic structure theory. Special emphasis is placed on the consistent treatment of time dependence and spin in the electronic wave function, as well as the inclusion of relativistic effects in said treatments. In addition, ChronusQ provides support for the inclusion of uniform finite magnetic fields as external perturbations through the use of gauge-including atomic orbitals. ChronusQ is a parallel electronic structure code written in modern C++ which utilizes both message passing implementation and shared memory (OpenMP) parallelism. In addition to the examination of the current state of code base itself, a discussion regarding ongoing developments and developer contributions will also be provided. This article is categorized under: Software > Quantum Chemistry Electronic Structure Theory > Ab Initio Electronic Structure Methods Electronic Structure Theory > Density Functional Theory.

Computation of intermolecular interactions is a challenge in drug discovery because accurate ab initio techniques are too computationally expensive to be routinely applied to drug–protein models. Classical force fields are more computationally feasible, and force fields designed to match symmetry adapted perturbation theory (SAPT) interaction energies can remain accurate in this context. Unfortunately, the application of such force fields is complicated by the laborious parameterization required for computations on new molecules. Here, we introduce the component-based machine-learned intermolecular force field (CLIFF), which combines accurate, physics-based equations for intermolecular interaction energies with machine-learning models to enable automatic parameterization. The CLIFF uses functional forms corresponding to electrostatic, exchange-repulsion, induction/polarization, and London dispersion components in SAPT. Molecule-independent parameters are fit with respect to SAPT2+(3)δMP2/aug-cc-pVTZ, and molecule-dependent atomic parameters (atomic widths, atomic multipoles, and Hirshfeld ratios) are obtained from machine learning models developed for C, N, O, H, S, F, Cl, and Br. The CLIFF achieves mean absolute errors (MAEs) no worse than 0.70 kcal mol−1 in both total and component energies across a diverse dimer test set. For the side chain–side chain interaction database derived from protein fragments, the CLIFF produces total interaction energies with an MAE of 0.27 kcal mol−1 with respect to reference data, outperforming similar and even more expensive methods. In applications to a set of model drug–protein interactions, the CLIFF is able to accurately rank-order ligand binding strengths and achieves less than 10% error with respect to SAPT reference values for most complexes. [ABSTRACT FROM AUTHOR]

A time-dependent (TD) formulation of equation-of-motion (EOM) coupled-cluster (CC) theory is developed, which, unlike other similar TD-EOM-CC approaches [D. R. Nascimento and A. E. DePrince III, J. Chem. Theory Comput. 12, 5834–5840 (2016)], can be applied to any type of linear electronic spectroscopy. The TD-EOM-CC method is formally equivalent to the standard frequency-domain formulation of EOM-CC theory, with a potential computational advantage of a comparatively low memory footprint. This general TD-EOM-CC framework is applied to the linear absorption and electric circular dichroism spectra of several small oxirane derivatives. [ABSTRACT FROM AUTHOR]

Ligand substitution reactions are common in solvated transition metal complexes, and harnessing them through initiation with light promises interesting practical applications, driving interest in new means of probing their mechanisms. Using a combination of time-resolved x-ray absorption spectroscopy and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics simulations and x-ray absorption near-edge spectroscopy calculations, we elucidate the mechanism of photoaquation in the model system iron(ii) hexacyanide, where UV excitation results in the exchange of a CN− ligand with a water molecule from the solvent. We take advantage of the high flux and stability of synchrotron x-rays to capture high precision x-ray absorption spectra that allow us to overcome the usual limitation of the relatively long x-ray pulses and extract the spectrum of the short-lived intermediate pentacoordinated species. Additionally, we determine its lifetime to be 19 (±5) ps. The QM/MM simulations support our experimental findings and explain the ∼20 ps time scale for aquation as involving interconversion between the square pyramidal (SP) and trigonal bipyramidal pentacoordinated geometries, with aquation being only active in the SP configuration. [ABSTRACT FROM AUTHOR]

We present a combined cavity quantum electrodynamics/ab initio electronic structure approach for simulating plasmon-molecule interactions in the time domain. The simple Jaynes-Cummings-type model Hamiltonian typically utilized in such simulations is replaced with one in which the molecular component of the coupled system is treated in a fully ab initio way, resulting in a computationally efficient description of general plasmon-molecule interactions. Mutual polarization effects are easily incorporated within a standard ground-state Hartree-Fock computation, and time-dependent simulations carry the same formal computational scaling as real-time time-dependent Hartree-Fock theory. As a proof of principle, we apply this generalized method to the emergence of a Fano-like resonance in coupled molecule-plasmon systems; this feature is quite sensitive to the nanoparticle-molecule separation and the orientation of the molecule relative to the polarization of the external electric field. [ABSTRACT FROM AUTHOR]

Variational two-electron reduced-density-matrix (2-RDM) methods can provide a reference-independent description of the electronic structure of strongly correlated molecules and materials. These methods represent one of few ways of performing large active-space-based computations that are beyond the scope of conventional configuration-interaction-based approaches. However, implementations of the method are quite rare, making it difficult for the quantum chemistry community to assess the utility of the approach. Here, we discuss an open-shell implementation of the variational 2-RDM method and explore its ability to describe different spin states in several model systems, including linear hydrogen chains and linear acenes. The largest calculations considered are comparable to complete-active-space computations with 50 electrons in 50 orbitals. [ABSTRACT FROM AUTHOR]

Source-to-sink systems are poorly known in tropical rivers. For the Amazonian rivers, the majority of the provenance studies remain focused on the suspended load, implying a poor understanding of the processes governing production and distribution of sands. In this study, we perform heavy mineral and optically stimulated luminescence (OSL) analysis to cover the entire spectrum (heavy and light minerals fraction) of 29 sand samples of the Lower Madeira river region (Amazon and Madeira rivers), of which the main goal was to find provenance indicators specific to these rivers. Despite the tropical humid climate, the sands of the Amazon and Lower Madeira rivers are rich in unstable heavy minerals as augite, hypersthene, green hornblende and andalusite. The Madeira river is highlighted by its higher content of andalusite, with source attributed to the Amazon Craton (medium-to-high grade metamorphic rocks), while the Amazon river, upstream of the Madeira river mouth, has a signature of augite and hypersthene, that suggests an Andean provenance (volcanic rocks). Sands from the Madeira river can be tracked in the Amazon river by the increasing concentration in andalusite. OSL analysis of the light minerals fraction was used as an index of feldspar concentration and sedimentary history of quartz grains. Lower feldspar concentration and quartz grains with longer sedimentary history (higher OSL sensitivity) also point to a major contribution of cratonic sources for the sands in the Madeira river. While the sands from the Lower Madeira would be mainly supplied by cratonic rocks, previous work recognised that suspended sediments (silt and clay) are derived from Andean rocks. Therefore, we interpret a decoupling between the sources of sand and mud (silt and clay) under transport in the Madeira river. Andean sands (rich in augite and hypersthene) would be trapped in the foreland zones of the Beni and Mamoré tributaries. In the Amazon river sands, the low OSL sensitivity of the quartz, higher content of feldspar and unstable heavy mineral assemblage dominated by augite and hypersthene suggest both a fast transport from Andean sources with fine sediment bypass over foreland areas. [ABSTRACT FROM AUTHOR]

The Chronus Quantum (ChronusQ) software package is an open source (under the GNU General Public License v2) software infrastructure which targets the solution of challenging problems that arise in ab initio electronic structure theory. Special emphasis is placed on the consistent treatment of time dependence and spin in the electronic wave function, as well as the inclusion of relativistic effects in said treatments. In addition, ChronusQ provides support for the inclusion of uniform finite magnetic fields as external perturbations through the use of gauge‐including atomic orbitals. ChronusQ is a parallel electronic structure code written in modern C++ which utilizes both message passing implementation and shared memory (OpenMP) parallelism. In addition to the examination of the current state of code base itself, a discussion regarding ongoing developments and developer contributions will also be provided. This article is categorized under:Software > Quantum ChemistryElectronic Structure Theory > Ab Initio Electronic Structure MethodsElectronic Structure Theory > Density Functional Theory [ABSTRACT FROM AUTHOR]

This paper presents an integration of the process of environmental licensing applied to Rio de Janeiro (Brazil) through the document Study and Report of Environmental Impact (EIA/RIMA). Also, the study analyzes the structuring of the recommendations of project management practices according to the Project Management Institute in the stages of initiation, planning, execution, control and closure. This is done to identify the efficiency in integration processes, stakeholders, scope, time, quality, cost and communication in the document project management plan EIA/RIMA. The contextualization of the national, state and local environmental licensing policies in Brazil was done. These are crucial in the making of the Environmental Impact Study. The integration of project management and environmental management documents contributes to form teams that are more committed with environmental responsibilities present in the work plans of environmental projects. [ABSTRACT FROM AUTHOR]