General Spin-Restricted Open-Shell Configuration Interaction Approach: Application to Metal K-Edge X-ray Absorption Spectra of Ferro- and Antiferromagnetically Coupled Dimers.

In this work, we present a generalized implementation of the previously developed restricted open-shell configuration interaction singles (ROCIS) family of methods. The new method allows us to treat high-spin (HS) ferro- as well as antiferromagnetically (AF) coupled systems while retaining the total spin as a good quantum number. To achieve this important and nontrivial goal, we employ the machinery of the iterative configuration expansion (ICE) method, which is able to tackle general configuration interaction (CI) problems on the basis of spin-adapted configuration state functions (CSFs).

Restricted Open-Shell Hartree-Fock Method for a General Configuration State Function Featuring Arbitrarily Complex Spin-Couplings.

In this work, we present a general spin restricted open-shell Hartree-Fock (ROHF) implementation that is able to generate self-consistent field (SCF) wave functions for an arbitrary configuration state function (CSF). These CSFs can contain an arbitrary number of unpaired electrons in arbitrary spin-couplings. The resulting method is named CSF-ROHF.

Methyl Ester Functionalized Phenalenyl Arene- and Bipyridine-Ruthenium-Based Complexes for Electroactive Langmuir-Blodgett Films.

We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1 H-phenalen-5-methyl carboxylate (L), and the generated complexes [Ru(bpy)L]PF and [(η-CH)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods, and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have an unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results.

DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole: Natural bond orbital method approach and a comprehensive energy decomposition analysis.

Penta(ammine)ruthenium benzotriazole complexes [Ru (NH ) bta] and [Ru (NH ) btaH] (bta and btaH are the deprotonated and neutral form of the triazole ligand, respectively) can exhibit two linkage isomers κN1 and κN2. This system was investigated by density functional theory natural bond orbitals analysis and Su-Li energy decomposition analysis. Steric, electrostatic, exchange, repulsion, polarization, and dispersion energy components of the total metal-ligand interaction were quantitatively evaluated, and revealed that the overall metal-triazole ligand is comprised of donor-acceptor interactions like σ-donation and π-back-donation, which favors a specific isomer depending on the oxidation state of the ruthenium and the charge of the ligand.