57 research outputs found
Accurate <i>ab initio</i> ro-vibronic spectroscopy of the X<sup>2</sup>∏ CCN radical using explicitly correlated methods
Explicitly correlated CCSD(T)-F12b calculations have been carried out with systematic sequences of correlation consistent basis sets to determine accurate near-equilibrium potential energy surfaces for the X<sup>2</sup>∏ and a<sup>4</sup>Σ<sup>â</sup> electronic states of the CCN radical. After including contributions due to core correlation, scalar relativity, and higher order electron correlation effects, the latter utilizing large-scale multireference configuration interaction calculations, the resulting surfaces were employed in variational calculations of the ro-vibronic spectra. These calculations also included the use of accurate spin-orbit and dipole moment matrix elements. The resulting ro-vibronic transition energies, including the Renner-Teller sub-bands involving the bending mode, agree with the available experimental data to within 3 cm<sup>â1</sup> in all cases. Full sets of spectroscopic constants are reported using the usual second-order perturbation theory expressions. Integrated absorption intensities are given for a number of selected vibronic band origins. A computational procedure similar to that used in the determination of the potential energy functions was also utilized to predict the formation enthalpy of CCN, ΔH<sub>f</sub>(0K) = 161.7 ± 0.5 kcal/mol
Ab initio wavefunction based methods for excited states in solids: correlation corrections to the band structure of ionic oxides
Ab initio wavefunction based methods are applied to the study of electron
correlation effects on the band structure of oxide systems. We choose MgO as a
prototype closed-shell ionic oxide. Our analysis is based on a local
Hamiltonian approach and performed on finite fragments cut from the infinite
solid. Localized Wannier functions and embedding potentials are obtained from
prior periodic Hartree-Fock (HF) calculations. We investigate the role of
various electron correlation effects in reducing the HF band gap and modifying
the band widths. On-site and nearest-neighbor charge relaxation as well as
long-range polarization effects are calculated. Whereas correlation effects are
essential for computing accurate band gaps, we found that they produce smaller
changes on the HF band widths, at least for this material. Surprisingly, a
broadening effect is obtained for the O 2p valence bands. The ab initio data
are in good agreement with the energy gap and band width derived from
thermoreflectance and x-ray photoemission experiments. The results show that
the wavefunction based approach applied here allows for well controlled
approximations and a transparent identification of the microscopic processes
which determine the electronic band structure
Orbital breathing effects in the computation of x-ray d-ion spectra in solids by ab initio wave-function-based methods
In existing theoretical approaches to core-level excitations of
transition-metal ions in solids relaxation and polarization effects due to the
inner core hole are often ignored or described phenomenologically. Here we set
up an ab initio computational scheme that explicitly accounts for such physics
in the calculation of x-ray absorption and resonant inelastic x-ray scattering
spectra. Good agreement is found with experimental transition-metal -edge
data for the strongly correlated cuprate LiCuO, for which we
determine the absolute scattering intensities. The newly developed methodology
opens the way for the investigation of even more complex electronic
structures of group VI B to VIII B correlated oxide compounds
Magnetic excitations and electronic interactions in SrCuTeO: a spin-1/2 square lattice Heisenberg antiferromagnet
SrCuTeO presents an opportunity for exploring low-dimensional
magnetism on a square lattice of Cu ions. We employ ab initio
multi-reference configuration interaction calculations to unravel the Cu
electronic structure and to evaluate exchange interactions in SrCuTeO.
The latter results are validated by inelastic neutron scattering using linear
spin-wave theory and series-expansion corrections for quantum effects to
extract true coupling parameters. Using this methodology, which is quite
general, we demonstrate that SrCuTeO is an almost realization of a
nearest-neighbor Heisenberg antiferromagnet but with relatively weak coupling
of 7.18(5) meV.Comment: 10 pages, 7 figure
Stability and Reversible Oxidation of Sub-Nanometric Cu5 Metal Clusters: Integrated Experimental Study and Theoretical Modeling**
Sub-nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude âbreathingâ motions. A chemical phase diagram for Cu oxidation states of the Cu5-oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu
The Molpro quantum chemistry package
Molpro is a general purpose quantum chemistry software package with a long development history. It was originally focused on accurate wavefunction calculations for small molecules but now has many additional distinctive capabilities that include, inter alia, local correlation approximations combined with explicit correlation, highly efficient implementations of single-reference correlation methods, robust and efficient multireference methods for large molecules, projection embedding, and anharmonic vibrational spectra. In addition to conventional input-file specification of calculations, Molpro calculations can now be specified and analyzed via a new graphical user interface and through a Python framework
Quantum study of inelastic processes in low-energy calciumâhydrogen collisions
International audienceCross-sections and rate coefficients for the partial inelastic processes in calciumâhydrogen collisions are calculated by means of the quantum reprojection method for nuclear dynamics based on the accurate ab initio electronic structure data. That is, the atomic data for the 110 inelastic processes of excitation, de-excitation, ion-pair formation, and mutual neutralization in Ca + H and Ca+ + Hâ collisions are computed for all transitions between the 11 low-lying CaH(2ÎŁ+) molecular states including ionic one. The quantum chemical data are used in a hybrid diabatic representation, which is derived from the adiabatic representation. It is found that the largest rate coefficients correspond to the mutual neutralization processes. At the temperature 6000âK, the maximal rate is equal to 4.37Ă10â8cm3sâ1â . It is shown that the large-valued rates are determined by long-range ionicâcovalent interactions with final binding energies from the optimal window, while moderate- and low-valued rates by both long- and short-range non-adiabatic regions with final energies outside of the optimal window
Stability of the HgS molecule and spectroscopy of its low lying electronic states
International audienceLarge scale Multireference Configuration Interactions (MRCI) and energy consistent relativistic pseudopotential (for the Hg atom) have been used to investigate the electronic structure, stability and spectroscopy of the low lying electronic states of the HgS molecule. The relative position of the two lowest electronic states, X-1 Sigma(+) and a(3)Pi, was found to be very sensitive to the quality of the basis set. Spin-orbit effects were taken into account leading to accurate spectroscopic data useful for the identification of the molecule. T-0 between the lowest components of the two states, X-1 Sigma(+)(0) and a(3)Pi(2), has been evaluated to be 0.142eV (3.5 kcal mol(-1)). Dipole moment functions were calculated for the lowest states; the rather large dipole moment of the X-1 Sigma(+) state makes possible the detection of vibrational transitions with a calculated ! e equal to 364cm(-1). Transitions between the X-1 Sigma(+) and the A(1)Pi states are predicted in the far IR domain with a T-0 = 5794cm(-1). The predissociation of the X-1 Sigma(+) and A(1)Pi states has been analysed and it has been shown that for the X-1 Sigma(+)(0) state only the vibrational levels below v = 11 are stable; higher levels are predissociated by the a(3)Pi(0) state. The effective dissociation energy of the X-1 Sigma(+)(0) state of HgS can thus be estimated to be 0.47eV (6.5 kcal mol(-1)). For the A(1)Pi state, the levels with v > 8 are predissociated by the dissociative b(3)Sigma(-) state
Inelastic processes in oxygenâhydrogen collisions
International audienceNew accurate theoretical rate coefficients for (de)-excitation and charge transfer in low-energy O + H, O+ + Hâ and Oâ + H+ collisions are reported. The calculations of cross-sections and rate coefficients are performed by means of the quantum probability current method, using full configuration interaction ab initio electronic structure calculations that provide a global description of all 43 lowest molecular states from short to asymptotic internuclear distances. Thus, both long- and short-range non-adiabatic regions are taken into account for the first time. All the doublet, quartet and sextet OH molecular states, with excitation energy asymptotes up to 12.07 eV, as well as the two lowest ionic states with the asymptotes OâH+ and O+Hâ are treated. Calculations are performed for the collision energy range 0.01â100eV and the temperature range 1â000â10â000 K. The mechanisms underlying the processes are analysed: it is shown that the largest rate coefficients, with values exceeding 10â8 cm3 sâ1, are due to ionicâcovalent interactions present at large internuclear distances, while short-range interactions play an important role for rates with moderate values involved in (de)-excitation processes. As a consequence, a comparison of the present data with previously published results shows that differences of up to several orders of magnitude exist for rate coefficients with moderate values. It is worth pointing out the relatively large rate coefficients for tripletâquintuplet oxygen transitions, as well as for transitions between the O(2p33s5So) and O(2p33p5P) levels of the oxygen triplet and H(n = 2) levels. The calculated data are important for modelling stellar spectra, leading to accurate oxygen abundances
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