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. Maintaining excellence in science is fundamental to the continuation of the U.S. as a global economic leader. Science provides a basis for solving important global challenges such as security, energy, climate, and health. Diverting funding from science into activities unrelated to the production of knowledge undermines science's ability to serve humankind. When funding agencies politicize science by using their power to further a particular ideological agenda, they contribute to public mistrust in science. Hijacking science funding to promote DEI is thus a threat to our society.

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. By using quantum chemistry calculations, we assess the extent of the coupling of the two OCCs with each other and the molecular scaffold. We show that promising coolable bi-OCC molecules can be proposed by following chemical design principles.

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. The character of the excimer state and the state responsible for the brightest transition are similar to those of the benzene dimer. The constrained structure of PCP allows one to focus on the most important degree of freedom, the inter-ring distance. The calculations explain the main features of the transient absorption spectral evolution. This brightest transition of the excimer is polarized along the inter-fragment axis. The absorption of the light polarized in the plane of the rings reveals the presence of other absorbing states of Rydberg character, with much weaker intensities. We also report new transient absorption data obtained by a broadband 8 fs pump, which time-resolve strong modulations of the excimer absorption. The combination of theory and experiment provides a detailed picture of the evolution of the electronic structure of the PCP excimer in the course of a single molecular vibration.

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 CO2 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. We also consider solvatochromic shifts and wave function characteristics. The latter is described by using reduced quantities such as natural transition orbitals (NTOs) and exciton descriptors. The functionals are benchmarked against the experimental fluorescence spectra and the equation-of-motion coupled-cluster method with single and double excitations. Both in isolated chromophores and in exciplexes, meta-GGA functionals drastically underestimate the emission energies and exhibit significant exciton delocalization and anticorrelation between electron and hole motion. The performance of global hybrid functionals is strongly dependent on the percentage of exact exchange. Our study identifies RSH GGAs as the best-performing functionals, with ωPBE demonstrating the best agreement with experimental results. RSH meta-GGAs often overestimate emission energies in exciplexes and yield larger hole NTOs. Their performance can be improved by optimally tuning the range-separation parameter.

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. Here we develop theoretical protocols based on coupled-cluster theory and electrostatic embedding. Our value of the intrinsic solvent-induced shift of the 1sO ionization energy of water is -1.79 eV. The computed absolute position and the width of the 1sO peak in photoelectron spectrum of water are 538.47 eV and 1.44 eV, respectively, agreeing well with the best experimental values.

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. The presented analysis explains the intensity patterns and attributes the differences between the 1PA and 2PA spectra to the native symmetry of isolated SCN - , which influences the spectra in the low-symmetry solvated environment. The native symmetry also manifests itself in variations of the polarization ratio (e.g., parallel vs. perpendicular cross sections) across the spectrum. The presented results highlight the potential of 2PA spectroscopy and high-level quantum-chemistry methods in studies of condensed-phase phenomena.