Ab Initio Study of the Vibrational Spectrum and Related Properties of Crystalline Compounds; the Case of CaCO3 Calcite
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Loredana Valenzano
Abstract
The static and high frequency dielectric tensors, Born effective charges, vibrational spectrum at the Γ point, TO-LO splitting and IR intensities of calcite CaCO3 have been calculated with the periodic ab initio CRYSTAL program, with five different basis sets of increasing size and four different Hamiltonians (HF, LDA, PBE, B3LYP). B3LYP is shown to perform better than the other options, in particular of LDA and PBE that are often used for the calculation of the vibrational spectrum of crystalline solids. When comparing B3LYP and experimental frequencies, the mean absolute difference is as small as 8.5 cm-1; this number reduces to 4.8 cm-1 if the two lowest experimental frequencies, that we suspect to be affected by a relatively large error, are excluded from statistics. Static and high frequency dielectric tensors, as well as IR intensities computed with the same hybrid scheme (B3LYP) compare quite favourably with experiment. The full set of modes is characterized by various tools including isotopic substitution, “freezing” one of the two subunits (Ca2+ or CO32-) and graphical representations. A general tool has been implemented, that permits the automatic generation of the animation of the full set of modes starting from the CRYSTAL output (available at www.crystal.unito.it/vibs/calcite).
© by Oldenbourg Wissenschaftsverlag, München
Articles in the same Issue
- Preface: Wolf Weyrich – a biography
- Comparison of the Proton Transfer Path in Hydrogen Bonds from Theoretical Potential Energy Surfaces and the Concept of Conservation of Bond Order
- Theoretical Study of Structure and Energetics of Gold Clusters with the EAM Method
- Crystal Spectrometers for Compton Scattering Studies
- Compton Profiles of Hydrated Na+ and F- Ions
- Wigner Functions and Bond Orders
- Structural and Magnetic Properties of [Mn3(C2H3O2)6(H2O)4]· 2(C2H5NO2)· 2(H2O)
- Ab Initio Study of the Vibrational Spectrum and Related Properties of Crystalline Compounds; the Case of CaCO3 Calcite
- On the Prospective Use of the One-Electron Density Matrix as a Test of the Quality of Post-Hartree–Fock Schemes for Crystals
- Generalized Hybrid Orbitals in the FA-ADMA Method
- Density-Matrix Study of the Hydrogen-Antihydrogen Molecule
- The Role of the Lone Pairs in Hydrogen Bonding
- Nuclear Inelastic Scattering on Ferrocene-Based Rotator Phases: Theory vs. Experiment
Articles in the same Issue
- Preface: Wolf Weyrich – a biography
- Comparison of the Proton Transfer Path in Hydrogen Bonds from Theoretical Potential Energy Surfaces and the Concept of Conservation of Bond Order
- Theoretical Study of Structure and Energetics of Gold Clusters with the EAM Method
- Crystal Spectrometers for Compton Scattering Studies
- Compton Profiles of Hydrated Na+ and F- Ions
- Wigner Functions and Bond Orders
- Structural and Magnetic Properties of [Mn3(C2H3O2)6(H2O)4]· 2(C2H5NO2)· 2(H2O)
- Ab Initio Study of the Vibrational Spectrum and Related Properties of Crystalline Compounds; the Case of CaCO3 Calcite
- On the Prospective Use of the One-Electron Density Matrix as a Test of the Quality of Post-Hartree–Fock Schemes for Crystals
- Generalized Hybrid Orbitals in the FA-ADMA Method
- Density-Matrix Study of the Hydrogen-Antihydrogen Molecule
- The Role of the Lone Pairs in Hydrogen Bonding
- Nuclear Inelastic Scattering on Ferrocene-Based Rotator Phases: Theory vs. Experiment
