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

Dissecting the Molecular Origin of <i>g</i> -Tensor Heterogeneity and Strain in Nitroxide Radicals in Water: Electron Paramagnetic Resonance Experiment versus Theory

Nitroxides are common EPR sensors of microenvironmental properties such as polarity, numbers of H-bonds, pH, and so forth. Their solvation in an aqueous environment is facilitated by their high propensity to form H-bonds with the surrounding water molecules. Their g- and A-tensor elements are key parameters to extracting the properties of their microenvironment. In particular, the gxx value of nitroxides is rich in information. It is known to be characterized by discrete values representing nitroxide populations previously assigned to have different H-bonds with the surrounding waters. Additionally, there is a large g-strain, that is, a broadening of g-values associated with it, which is generally correlated with environmental and structural micro-heterogeneities. The g-strain is responsible for the frequency dependence of the apparent line width of the EPR spectra, which becomes evident at high field/frequency. Here, we address the molecular origin of the gxx heterogeneity and of the g-strain of a nitroxide moiety (HMI: 2,2,3,4,5,5-hexamethylimidazolidin-1-oxyl, C9H19N2O) in water. To treat the solvation effect on the g-strain, we combined a multi-frequency experimental approach with ab initio molecular dynamics simulations for structural sampling and quantum chemical EPR property calculations at the highest realistically affordable level, including an explicitly micro-solvated HMI ensemble and the embedded cluster reference interaction site model. We could clearly identify the distinct populations of the H-bonded nitroxides responsible for the gxx heterogeneity experimentally observed, and we dissected the role of the solvation shell, H-bond formation, and structural deformation of the nitroxide in the creation of the g-strain associated with each nitroxide subensemble. Two contributions to the g-strain were identified in this study. The first contribution depends on the number of hydrogen bonds formed between the nitroxide and the solvent because this has a large and well-understood effect on the gxx-shift. This contribution can only be resolved at high resonance frequencies, where it leads to distinct peaks in the gxx region. The second contribution arises from configurational fluctuations of the nitroxide that necessarily lead to g-shift heterogeneity. These contributions cannot be resolved experimentally as distinct resonances but add to the line broadening. They can be quantitatively analyzed by studying the apparent line width as a function of microwave frequency. Interestingly, both theory and experiment confirm that this contribution is independent of the number of H-bonds. Perhaps even more surprisingly, the theoretical analysis suggests that the configurational fluctuation broadening is not induced by the solvent but is inherently present even in the gas phase. Moreover, the calculations predict that this broadening decreases upon solvation of the nitroxide.</p

The enthalpies of formation of AsXn molecules, where X= H, F, or Cl, and n=1,2 or 3 by RCCSD(T) and UCCSD(T)-F12x calculations

RCCSD(T) and UCCSD(T)-F12x calculations were performed on AsXn molecules, where X = H, F or Cl, and n = 1, 2 or 3, and related species, in order to evaluate their enthalpies of formation (?HfØ). The recommended ?HfØ values obtained from the present investigation are AsH, 57.7(2); AsF, ?7.9(3); AsCl, 27.2(4); AsH2, 39.8(4); AsF2, ?96.6(9); AsCl2, ?17.8(10); AsH3, 17.1(4); AsF3 ?196.0(5) and AsCl3, ?59.1(27) kcal mole?1. These values are anchored only on one thermodynamic quantity, namely, ?HfØ(As) (= 70.3 kcal mole?1). In the calculations, the fully-relativistic small-core effective core potential (ECP10MDF) was used for As. Contributions from outer core correlation of As 3d10 electrons were computed explicitly in both RCCSD(T) and UCCSD(T)-F12 calculations with additional tight basis functions designed for As 3d10 electrons. Basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality were used in RCCSD(T) calculations and computed relative electronic energies were extrapolated to the complete basis set (CBS) limit. For the simplified, explicitly correlated UCCSD(T)-F12x calculations, basis sets of up to quadruple-zeta (QZ) quality were employed. Based on the RCCSD(T)/CBS benchmark values, the reliability of available theoretical and experimental values have been assessed.<br/

The Tokyo Olympic Games 2020, its role for influencing the perceptions held by the world on the governmental attitude toward the nuclear power plant problem, and re-branding the image of Japan

Theoretical predictions show that depending on the populations of the Fe 3d_<i>xy</i>, 3d_<i>xz</i>, and 3d_<i>yz</i> orbitals two possible quintet states can exist for the high-spin state of the photoswitchable model system [Fe­(terpy)₂]²⁺. The differences in the structure and molecular properties of these ⁵B₂ and ⁵E quintets are very small and pose a substantial challenge for experiments to resolve them. Yet for a better understanding of the physics of this system, which can lead to the design of novel molecules with enhanced photoswitching performance, it is vital to determine which high-spin state is reached in the transitions that follow the light excitation. The quintet state can be prepared with a short laser pulse and can be studied with cutting-edge time-resolved X-ray techniques. Here we report on the application of an extended set of X-ray spectroscopy and scattering techniques applied to investigate the quintet state of [Fe­(terpy)₂]²⁺ 80 ps after light excitation. High-quality X-ray absorption, nonresonant emission, and resonant emission spectra as well as X-ray diffuse scattering data clearly reflect the formation of the high-spin state of the [Fe­(terpy)₂]²⁺ molecule; moreover, extended X-ray absorption fine structure spectroscopy resolves the Fe–ligand bond-length variations with unprecedented bond-length accuracy in time-resolved experiments. With <i>ab initio</i> calculations we determine why, in contrast to most related systems, one configurational mode is insufficient for the description of the low-spin (LS)–high-spin (HS) transition. We identify the electronic structure origin of the differences between the two possible quintet modes, and finally, we unambiguously identify the formed quintet state as ⁵E, in agreement with our theoretical expectations

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 300 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 776 entries, the paper represents a broad snapshot of DFT, anno 2022

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 300 individual contributions, formulated as responses to a preset list of 26 questions. Supported by a bibliography of 776 entries, the paper represents a broad snapshot of DFT, anno 2022