Photoswitching Molecules Functionalized with Optical Cycling Centers Provide a Novel Platform for Studying Chemical Transformations in Ultracold Molecules.

A novel molecular structure that bridges the fields of molecular optical cycling and molecular photoswitching is presented. It is based on a photoswitching molecule azobenzene functionalized with one and two CaO- groups, which can act as optical cycling centers (OCCs). This paper characterizes the electronic structure of the resulting model systems, focusing on three questions: (1) how the electronic states of the photoswitch are impacted by a functionalization with an OCC; (2) how the states of the OCC are impacted by the scaffold of the photoswitch; and (3) whether the OCC can serve as a spectroscopic probe of isomerization.

Vibronic Coupling Effects in the Photoelectron Spectrum of Ozone: A Coupled-Cluster Approach.

One of the most important areas of application for equation-of-motion coupled-cluster (EOM-CC) theory is the prediction, simulation, and analysis of various types of electronic spectra. In this work, the EOM-CC method for ionized states, known as EOM-IP-CC, is applied to the closely lying and coupled pair of states of the ozone cation─ and ─using highly accurate treatments including up to the full single, double, triple, and quadruple excitations (EOM-IP-CCSDTQ). Combined with a venerable and powerful method for calculating vibronic spectra from the Hamiltonian produced by EOM-IP-CC calculations, the simulations yield a spectrum that is in good agreement with the photoelectron spectrum of ozone.

Politicizing science funding undermines public trust in science, academic freedom, and the unbiased generation of knowledge.

This commentary documents how federal funding agencies are changing the criteria by which they distribute taxpayer money intended for scientific research. Increasingly, STEMM (Science, Technology, Engineering, Mathematics, and Medicine) funding agencies are requiring applicants for funding to include a plan to advance DEI ("Diversity, Equity, and Inclusion") in their proposals and to dedicate a part of the research budget to its implementation. These mandates undermine the academic freedom of researchers and the unbiased generation of knowledge needed for a well-functioning democracy.

Dual Optical Cycling Centers Mounted on an Organic Scaffold: New Insights from Quantum Chemistry Calculations and Symmetry Analysis.

Molecules cooled to ultracold temperatures are desirable for applications in fundamental physics and quantum information science. However, cooling polyatomic molecules with more than six atoms has not yet been achieved. Building on the idea of an optical cycling center (OCC), a moiety supporting a set of localized and isolated electronic states within a polyatomic molecule, molecules with two OCCs (bi-OCCs) may afford better cooling efficiency by doubling the photon scattering rate.

Revisiting the benzene excimer using [2,2] paracyclophane model system: Experiment and theory.

We report high-level calculations of the excited states of [2,2]-paracyclophane (PCP), which was recently investigated experimentally by ultrafast pump-probe experiments on oriented single crystals [Haggag et al., ChemPhotoChem 6 e202200181 (2022)]. PCP, in which the orientation of the two benzene rings and their range of motion are constrained, serves as a model for studying benzene excimer formation.

Performance of Density Functionals for Excited-State Properties of Isolated Chromophores and Exciplexes: Emission Spectra, Solvatochromic Shifts, and Charge-Transfer Character.

This study assesses the performance of various meta-generalized gradient approximation (meta-GGA), global hybrid, and range-separated hybrid (RSH) density functionals in capturing the excited-state properties of organic chromophores and their excited-state complexes (exciplexes). Motivated by their uses in solar energy harvesting and photoredox CO reduction, we use oligo-(p-phenylenes) and their excited-state complexes with triethylamine as model systems. We focus on the fluorescence properties of these systems, specifically emission energies.

Core-ionization spectrum of liquid water.

We present state-of-the-art calculations of the core-ionization spectrum of water. Despite significant progress in procedures developed to mitigate various experimental complications and uncertainties, the experimental determination of ionization energies of solvated species involves several non-trivial steps such as assessing the effect of the surface potential, electrolytes, and finite escape depths of photoelectrons. This provides a motivation to obtain robust theoretical values of the intrinsic bulk ionization energy and the corresponding solvent-induced shift.

Two- and one-photon absorption spectra of aqueous thiocyanate anion highlight the role of symmetry in the condensed phase.

We present the two-photon absorption (2PA) spectrum of aqueous thiocyanate calculated using high-level quantum-chemistry methods. The 2PA spectrum is compared to the one-photon absorption (1PA) spectrum computed using the same computational protocol. Although the two spectra probe the same set of electronic states, the intensity patterns are different, leading to an apparent red-shift of the 2PA spectrum relative to the 1PA spectrum.

Prosocial motives underlie scientific censorship by scientists: A perspective and research agenda.

Science is among humanity's greatest achievements, yet scientific censorship is rarely studied empirically. We explore the social, psychological, and institutional causes and consequences of scientific censorship (defined as actions aimed at obstructing particular scientific ideas from reaching an audience for reasons other than low scientific quality). Popular narratives suggest that scientific censorship is driven by authoritarian officials with dark motives, such as dogmatism and intolerance.

State-Interaction Approach for Evaluating -Tensors within EOM-CC and RAS-CI Frameworks: Theory and Benchmarks.

Among various techniques designed for studying open-shell species, electron paramagnetic resonance (EPR) spectroscopy plays an important role. The key quantity measured by EPR is the -tensor, describing the coupling between an external magnetic field and molecular electronic spin. One theoretical framework for quantum chemistry calculations of -tensors is based on response theory, which involves substantial developments that are specific to the underlying electronic structure models.

Molecular-Orbital Framework of Two-Electron Processes: Application to Auger and Intermolecular Coulomb Decay.

States with core- or inner-shell vacancies, which are commonly created by absorption of high-energy photons, can decay by a two-electron process in which one electron fills the core hole and the second one is ejected. These processes accompany many X-ray spectroscopies. Depending on the nature of the initial core- or inner-shell-hole state and the decay valence-hole state, these processes are called Auger decay, intermolecular Coulomb decay, or electron-transfer-mediated decay.

Analytic Evaluation of Nonadiabatic Couplings within the Complex Absorbing Potential Equation-of-Motion Coupled-Cluster Method.

We present the theory for the evaluation of nonadiabatic couplings (NACs) involving resonance states within the complex absorbing potential equation-of-motion coupled-cluster (CAP-EOM-CC) framework implemented within the singles and doubles approximation. Resonance states are embedded in the continuum and undergo rapid decay through autodetachment. In addition, nuclear motion can facilitate transitions between different resonances and between resonances and bound states.

Simulating excited-state complex ensembles: Fluorescence and solvatochromism in amine-arene exciplexes.

Exciplexes are excited-state complexes formed as a result of partial charge transfer from the donor to the acceptor species when one moiety of the donor-acceptor pair is electronically excited. The arene-amine exciplex formed between oligo-(p-phenylene) (OPP) and triethylamine (TEA) is of interest in the catalytic photoreduction of CO2 because it can compete with complete electron transfer to the OPP catalyst. Therefore, formation of the exciplex can hinder the generation of a radical anion OPP·- necessary for subsequent CO2 reduction.

Two Algorithms for Excited-State Quantum Solvers: Theory and Application to EOM-UCCSD.

Near-term quantum devices promise to revolutionize quantum chemistry, but simulations using the current noisy intermediate-scale quantum (NISQ) devices are not practical due to their high susceptibility to errors. This motivated the design of NISQ algorithms leveraging classical and quantum resources. While several developments have shown promising results for ground-state simulations, extending the algorithms to excited states remains challenging.

Multiscale Simulations of the Covalent Inhibition of the SARS-CoV-2 Main Protease: Four Compounds and Three Reaction Mechanisms.

We report the results of computational modeling of the reactions of the SARS-CoV-2 main protease (M) with four potential covalent inhibitors. Two of them, carmofur and nirmatrelvir, have shown experimentally the ability to inhibit M. Two other compounds, X77A and X77C, were designed computationally in this work.

Influence of Transition Metal Electron Configuration on the Structure of Metal-EDTA Complexes.

The vibrational spectra of cold complexes of ethylenediaminetetraacetic acid (EDTA) with transition metal dications in vacuo show how the electronic structure of the metal provides a geometric template for interaction with the functional groups of the binding pocket. The OCO stretching modes of the carboxylate groups of EDTA serve as structural probes, informing on the spin state of the ion as well as the coordination number in the complex. The results highlight the flexibility of EDTA in accepting a large range of metal cations in its binding site.

The Auger spectrum of benzene.

We present an ab initio computational study of the Auger electron spectrum of benzene. Auger electron spectroscopy exploits the Auger-Meitner effect, and although it is established as an analytic technique, the theoretical modeling of molecular Auger spectra from first principles remains challenging. Here, we use coupled-cluster theory and equation-of-motion coupled-cluster theory combined with two approaches to describe the decaying nature of core-ionized states: (i) Feshbach-Fano resonance theory and (ii) the method of complex basis functions.

Theory, implementation, and disappointing results for two-photon absorption cross sections within the doubly electron-attached equation-of-motion coupled-cluster framework.

The equation-of-motion coupled-cluster singles and doubles method with double electron attachment (EOM-DEA-CCSD) is capable of computing reliable energies, wave functions, and first-order properties of excited states in diradicals and polyenes that have a significant doubly excited character with respect to the ground state, without the need for including the computationally expensive triple excitations. Here, we extend the capabilities of the EOM-DEA-CCSD method to the calculations of a multiphoton property, two-photon absorption (2PA) cross sections. Closed-form expressions for the 2PA cross sections are derived within the expectation-value approach using response wave functions.

Signatures of the Bromine Atom and Open-Shell Spin Coupling in the X-ray Spectrum of the Bromobenzene Cation.

Tabletop X-ray spectroscopy measurements at the carbon -edge complemented by calculations are used to investigate the influence of the bromine atom on the carbon core-valence transitions in the bromobenzene cation (BrBz). The electronic ground state of the cation is prepared by resonance-enhanced two-photon ionization of neutral bromobenzene (BrBz) and probed by X-rays produced by high-harmonic generation (HHG). Replacing one of the hydrogen atoms in benzene with a bromine atom shifts the transition from the 1s orbital of the carbon atom (C*) bonded to bromine by ∼1 eV to higher energy in the X-ray spectrum compared to the other carbon atoms (C).

Spin-orbit couplings within spin-conserving and spin-flipping time-dependent density functional theory: Implementation and benchmark calculations.

We present a new implementation for computing spin-orbit couplings (SOCs) within a time-dependent density-functional theory (TD-DFT) framework in the standard spin-conserving formulation as well in the spin-flip variant (SF-TD-DFT). This approach employs the Breit-Pauli Hamiltonian and Wigner-Eckart's theorem applied to the reduced one-particle transition density matrices, together with the spin-orbit mean-field treatment of the two-electron contributions. We use a state-interaction procedure and compute the SOC matrix elements using zero-order non-relativistic states.

Spectroscopic signatures of states in the continuum characterized by a joint experimental and theoretical study of pyrrole.

We report a combined experimental and theoretical investigation of electron-molecule interactions using pyrrole as a model system. Experimental two-dimensional electron energy loss spectra (EELS) encode information about the vibrational states of the molecule as well as the position and structure of electronic resonances. The calculations using complex-valued extensions of equation-of-motion coupled-cluster theory (based on non-Hermitian quantum mechanics) facilitate the assignment of all major EELS features.

DFT exchange: sharing perspectives on the workhorse of quantum chemistry and materials science.

In this paper, the history, present status, and future of density-functional theory (DFT) is informally reviewed and discussed by 70 workers in the field, including molecular scientists, materials scientists, method developers and practitioners. The format of the paper is that of a roundtable discussion, in which the participants express and exchange views on DFT in the form of 302 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 777 entries, the paper represents a broad snapshot of DFT, anno 2022.