Multi--Occupancy as an Alternative Definition for the Double -Shell Effect.

Despite the prevalence of first-row transition metal-containing compounds in virtually all areas of chemistry, the accurate modeling of these systems is a known challenge for the theoretical chemistry community. Such a challenge is shown in a myriad of facets; among them are difficulties in defining ground-state multiplicities, disagreement in the results from methods considered highly accurate, and convergence problems in calculations for excited states. These problems cause a scarcity of reliable theoretical data for transition metal-containing systems.

Diving into the optoelectronic properties of Cu(II) and Zn(II) curcumin complexes: a DFT and wavefunction benchmark.

Context: Curcumin is a popular food additive around the world whose medicinal properties have been known since ancient times. The literature has recently highlighted several biological properties, but besides the health-related usages, its natural yellowish color may also be helpful for light-harvesting applications. This research aims to close a knowledge gap regarding the photophysical description of curcumin and its metallic complexes.

Geometric interpretation for coupled-cluster theory. A comparison of accuracy with the corresponding configuration interaction model.

Although coupled-cluster theory is well-known for its accuracy, the geometry associated with the manifold of wave functions reached by the coupled-cluster Ansatz has not been deeply explored. In this article, we look for an interpretation for the high accuracy of coupled-cluster theory based on how the manifold of coupled-cluster wave functions is embedded within the space of n-electron wave functions. We define the coupled-cluster and configuration interaction manifolds and measure the distances from the full-configuration interaction (FCI) wave function to these manifolds.

Can one use the electronic absorption spectra of metalloporphyrins to benchmark electronic structure methods? A case study on the cobalt porphyrin.

In this article, we describe calculations on the absorption spectrum of cobalt(ii) porphyrin, using density functional (DFT) and multireference n-electron valence perturbation (NEVPT) theories. With these calculations, we describe the lowest-energy states of doublet and quartet spin multiplicities, the excited states that originate the Q and B bands of porphyrins, some higher-energy π-π* excitations and charge-transfer states, HOMO-LUMO gaps, and ionisation potentials. Results undoubtedly show that the position of B band is essentially independent on the DFT functional, while the Q band is better described by pure functionals, and these bands do not depend on the initial state of the transition (whether doublet or quartet) as well.

Perturbation Expansion of Internally Contracted Coupled-Cluster Theory up to Third Order.

The internally contracted multireference coupled-cluster (icMRCC) method is analyzed through third order in perturbation theory. Up to second order, the icMRCC perturbation expansion is equivalent to that of the standard Rayleigh-Schrödinger perturbation theory, which is based on a linear ansatz for the wave function, and the resulting theory is, depending on the employed zeroth-order Hamiltonian, equivalent to either second-order complete active space perturbation theory (CASPT2), N-electron valence perturbation theory (NEVPT2), or Fink's retention of the excitation degree perturbation theory (REPT2). At third order, the icMRCC perturbation expansion features additional terms in comparison to the Rayleigh-Schrödinger perturbation theory, but these are shown to be nearly negligibly small by both analytic arguments and numerical examples.

Revisiting the F + HCl → HF + Cl reaction using a multireference coupled-cluster method.

We have constructed a new potential energy surface for the title reaction, based on the internally contracted multireference coupled-cluster method. The calculated barrier height is 1.59 ± 0.

Internally contracted multireference coupled-cluster theory in a multistate framework.

The internally contracted multireference coupled cluster (icMRCC) theory is reexamined in a multistate framework. The new derivation starts from the Bloch equations employing a wave operator similar to the one originally employed by Jeziorski and Monkhorst [Phys. Rev.

Metastable BrO2+ and NBr2+ molecules in the gas phase.

The doubly positively charged gas-phase molecules BrO(2+) and NBr(2+) have been produced by prolonged high-current energetic oxygen (17 keV (16)O(-)) ion surface bombardment (ion beam sputtering) of rubidium bromide (RbBr) and of ammonium bromide (NH(4)Br) powdered ionic salt samples, respectively, pressed into indium foil. These novel species were observed at half-integer m∕z values in positive ion mass spectra for ion flight times of roughly ∼12 μs through a magnetic-sector secondary ion mass spectrometer. Here we present these experimental results and combine them with a detailed theoretical investigation using high level ab initio calculations of the ground states of BrO(2+) and NBr(2+), and a manifold of excited electronic states.

New molecular species of potential interest to atmospheric chemistry: isomers on the [H, S2, Br] potential energy surface.

This work reports a state-of-the-art theoretical characterization of four new sulfur-bromine species and five transition states on the [H, S(2), Br] potential energy surface. Our highest level theoretical approach employed the method coupled cluster singles and doubles with perturbative contributions of connected triples, CCSD(T), along with the series of correlation-consistent basis sets and with extrapolation to the complete basis set (CBS) limit in the optimization of the geometrical parameters and to quantify the energetic quantities. The structural and vibrational frequencies here reported are unique and represent the most accurate investigation to date of these species.

Predicting new molecular species of potential interest to atmospheric chemistry: the isomers HSBr and HBrS.

Coupled cluster singles and doubles with perturbative contributions of connected triples CCSD(T) theory with a series of correlation consistent basis sets was used to predict the existence and characterize for the first time the structures, harmonic frequencies, and energetic quantities of the isomeric species HSBr and HBrS, as well as the transition state connecting them. These calculations consider extrapolation to the complete basis set (CBS) limit, corrections for scalar relativistic effects using the second-order Douglas-Kroll-Hess Hamiltonian, and also correlation of the bromine d electrons in addition to the 14 valence electrons. The species HSBr was found to be more stable than HBrS by 50.