RESUMO
The reactivity of diatomic titanium with nitrous oxide has been studied in solid neon. Two molecules with the same Ti2-N2O stoichiometry are identified from concentration, temperature, and irradiation effects. The more stable one is characterized by five fundamental vibrational transitions located below 1000 cm(-1), the high frequency one at 946 cm(-1) corresponding to a pure TiO stretching mode. Its structure, a rhombus OTiNTiN with the extra O atom fixed on one Ti, is confirmed by quantum chemical calculations, at the CCSD(T) level, which predict a Cs structure in the singlet state with a Ti-O bond length close to 1.66 Å, two nonequivalent Ti-N distances close to 1.94 and 1.75 Å, and a OTiTi angle of 119.2°. The second Ti2-N2O molecule, only observed after annealing, is easily converted into the first one upon irradiation above 12 000 cm(-1) and its kinetics of photoconversion allows vibrational transitions to be identified. The strongest one located at 2123.4 cm(-1) characterizes an N-N stretching mode. Corresponding ab initio calculations complete this picture with details on the electronic structure and allow us to identify a most adequate density functional to describe the spectroscopic properties of the studied species in a simpler broken-symmetry open-shell DFT context. The theoretical results predict the existence of a metastable product OTi2N2 and correctly account for the observed spectra of the various isotopic varieties.
RESUMO
The spectrum arising from the (π*)(2) configuration of the chalcogen dimers, namely, the X(2)1, a2, and b0(+) states, is calculated using wave-function theory based methods. Two-component (2c) and four-component (4c) multireference configuration interaction (MRCI) and Fock-space coupled cluster (FSCC) methods are used as well as two-step methods spin-orbit complete active space perturbation theory at 2nd order (SO-CASPT2) and spin-orbit difference dedicated configuration interaction (SO-DDCI). The energy of the X(2)1 state corresponds to the zero-field splitting of the ground state spin triplet. It is described with high accuracy by the 2- and 4-component methods in comparison with experiment, whereas the two-step methods give about 80% of the experimental values. The b0(+) state is well described by 4c-MRCI, SO-CASPT2, and SO-DDCI, but FSCC fails to describe this state and an intermediate Hamiltonian FSCC ansatz is required. The results are readily rationalized by a two-parameter model; Δε, the π* spinor splitting by spin-orbit coupling and K, the exchange integral between the π(1)* and the π(-1)* spinors with, respectively, angular momenta 1 and -1. This model holds for all systems under study with the exception of Po(2).
RESUMO
It has been widely accepted in the past that the g tensor describing the Zeeman splitting of a Kramers doublet is not uniquely defined. Here we show that with two basic requirements, (i) the invariance of the Zeeman Hamiltonian under symmetry transformations and (ii) its continuous change with the variations of the parameters of the system (geometry and crystal field), a unique determination of the elements of the g tensor is achieved.
RESUMO
An investigation of the sub-millimeter-wave spectra of the ionic complexes Ar.H+3 and Ar.D+3 is presented. These complexes were produced in a negative glow electric discharge, in mixtures of argon with either H2 or D2. About 80 new transitions were assigned in the 485-680 GHz frequency range using a sub-millimeter-wave spectrometer built with Russian made backward wave oscillators (BWO) sources. These measurements enabled us to observe the first Ka = 2 transitions for Ar.H+3 and the first Ka = 3 transitions for Ar.D+3. Analyses of the line frequencies were carried out using an IAM-like approach, which accounts for the large amplitude internal rotation motion displayed by both species. Insights into the geometry of the intermediate configuration for this large amplitude motion were gained. Copyright 1998 Academic Press.
