Search results for " ab initio"

Characterization of the pressure induced Ringwoodite toMg-perovskite and Mg-wüstite phase transition by Catastrophe Theory

2010

The pressure-induced ringwoodite to Mg-perovskite and periclase post-spinel phase transition: a Bader’s topological analysis of the ab initio electro…

2011

In order to characterize the pressure-induced decomposition of ringwoodite (c-Mg2SiO4), the topological analysis of the electron density q(r), based upon the theory of atoms in molecules (AIM) developed by Bader in the framework of the catastrophe theory, has been performed. Calculations have been carried out by means of the ab initio CRYSTAL09 code at the HF/DFT level, using Hamiltonians based on the Becke- LYP scheme containing hybrid Hartree– Fock/density functional exchange–correlation terms. The equation of state at 0 K has been constructed for the three phases involved in the post-spinel phase transition (ringwoodite -> Mg-perovskite + periclase) occurring at the transition zone–lower…

Theoretical study of the low‐lying states of trans‐1,3‐butadiene

1992

We present extensive ab initio calculations on the low‐lying electronic states of trans‐1,3‐butadiene within the multireference configuration interaction (MRCI) framework by selecting the configurations with a perturbative criterion. The X 1Ag ground state and 1 3Bu, 1 3Ag, 2 1Ag, and 1 1Bu valence excited states have been calculated at a fixed geometry. The results obtained are in good agreement with previous experimental and calculated values, and could help to understand polyene spectroscopy, photochemistry, and photophysics. The advantages of a MRCI method where the most important contributions to the total MRCI wave function, perturbatively selected, are treated variationally, and the …

Modelling of thermo-chemical properties over the sub-solidus MgO–FeO binary, as a function of iron spin configuration, composition and temperature

2014

Thermo-chemical properties and T–X phase relations diagram of the (Mg,Fe)O solid solution are modelled using mixing Helmholtz energy, ΔF(T,x)mixing, calculated by quantum mechanical and semi-empirical techniques. The sub-solidus MgO–FeO binary has been explored as a function of composition, with iron either in high-spin (HS) or low-spin (LS) configuration. Only the HS model provides physically sound results at room pressure, yielding a correct trend of cell edge versus composition, whereas LS’s issues are at variance with observations. Mixing Helmholtz energy has been parametrized by the following relationship: ΔF(T,x)mixing = x × y × [U0(T) + U1(T) × (x – y) + U2(T) × (x − y)2]−T × S(x,y)c…

Ab initio determination of the ionization potentials of DNA and RNA nucleobases

2006

Quantum chemical high level ab initio coupled-cluster and multiconfigurational perturbation methods have been used to compute vertical and adiabatic ionization potentials of the five canonical DNA and RNA nucleobases: uracil, thymine, cytosine, adenine, and guanine. Several states of their cations have been also calculated. The present results represent a systematic compendium of these magnitudes, establishing theoretical reference values at a level not reported before, calibrating computational strategies, and guiding the assignment of the features in the experimental photoelectron spectra. Daniel.Roca@uv.es Mercedes.Rubio@uv.es Manuela.Merchan@uv.es Luis.Serrano@uv.es

High-pressure structural, elastic, and thermodynamic properties of zircon-type HoPO4 and TmPO4

2017

[EN] Zircon-type holmium phosphate (HoPO4) and thulium phosphate (TmPO4) have been studied by single-crystal x-ray diffraction and ab initio calculations. We report on the influence of pressure on the crystal structure, and on the elastic and thermodynamic properties. The equation of state for both compounds is accurately determined. We have also obtained information on the polyhedral compressibility which is used to explain the anisotropic axial compressibility and the bulk compressibility. Both compounds are ductile and more resistive to volume compression than to shear deformation at all pressures. Furthermore, the elastic anisotropy is enhanced upon compression. Finally, the calculation…

Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene

1993

A newly proposed quantum chemical approach for ab initio calculations of electronic spectra of molecular systems is applied to the molecules ethene, trans‐1,3‐butadiene, and trans‐trans‐1,3,5‐hexatriene. The method has the aim of being accurate to better than 0.5 eV for excitation energies and is expected to provide structural and physical data for the excited states with good reliability. The approach is based on the complete active space (CAS) SCF method, which gives a proper description of the major features in the electronic structure of the excited state, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic ele…

Electron-density critical points analysis and catastrophe theory to forecast structure instability in periodic solids

2018

The critical points analysis of electron density,i.e. ρ(x), fromab initiocalculations is used in combination with the catastrophe theory to show a correlation between ρ(x) topology and the appearance of instability that may lead to transformations of crystal structures, as a function of pressure/temperature. In particular, this study focuses on the evolution of coalescing non-degenerate critical points,i.e. such that ∇ρ(xc) = 0 and λ1, λ2, λ3≠ 0 [λ being the eigenvalues of the Hessian of ρ(x) atxc], towards degenerate critical points,i.e. ∇ρ(xc) = 0 and at least one λ equal to zero. The catastrophe theory formalism provides a mathematical tool to model ρ(x) in the neighbourhood ofxcand allo…

Molecular dynamics simulations of elementary chemical processes in liquid water using combined density functional and molecular mechanics potentials.…

1997

The first molecular dynamics (MD) simulation of a chemical process in solution with an ab initio description of the reactant species and a classical representation of the solvent is presented. We study the dynamics of proton (deuterium) transfer in strongly hydrogen-bonded systems characterized by an energy surface presenting a double well separated by a low activation barrier. We have chosen the hydroxyl-water complex in liquid water to analyze the coupling between the reactive system and the environment. The proton is transferred from one well to the other with a frequency close to 1 ps−1 which is comparable to the low-frequency band associated to hindered translations, diffusional transl…

Vibrational Signature of Water Molecules in Asymmetric Hydrogen Bonding Environments

2013

The O–H stretching vibrational modes of water molecules are sensitive to their local environments. Here, we applied effective normal-mode analysis to isolate contributions of each of the two hydrogen atoms to the vibrational modes ν1 and ν3 of water molecules in the liquid phase. We demonstrate that the decoupling of the two contributions fd and the frequency splitting of the vibrational modes Δω13 are inextricably related to the symmetry of the hydrogen bonding environment. We show that ambient liquid water modeled at the density functional level of theory exhibits the characteristics of an asymmetric environment with an average decoupling of 0.82 and a splitting of 137 inverse centimeters…