Equilibrium structure of methylcyanide

The quadratic and cubic force fields of methylcyanide have been calculated at the MP2 and CCSD(T) levels of theory employing a core-valence basis set of triple-zeta quality. Semi-experimental equilibrium structures have then been derived from the experimental ground-state rotational constants available for various isotopologues and the corresponding vibrational corrections calculated from the ab initio force fields. These structures have been found in excellent agreement with the pure ab initio structure calculated at the CCSD(T) level of theory using a basis set of sextuple-zeta quality and including core correlation corrections.     

Ab initio anharmonic force field and equilibrium structure of propene

The quadratic, cubic and semi-diagonal quartic force field of propene has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-ζ quality and a core correlation correction. The experimental mass-dependent r_m structures are also determined and their accuracy is discussed. The use of isolated CH stretching frequencies is shown to be a good method to determine CH bond length.     

Ground-state constants, ab initio anharmonic force field, and equilibrium structure of F2BOH

The millimeterwave spectra of F₂¹⁰BOH and F₂¹¹BOH (difluorohydroxyborane) have been measured in their ground vibrational state. Accurate rotational and centrifugal distortion constants have been determined. The equilibrium geometry and anharmonic force fields have been calculated at the CCSD(T) level of theory. The ab initio centrifugal distortion constants and rotation-vibration interaction constants are compared to the experimental values. Some discrepancies are found and discussed. Particularly, it is explained why the semi-experimental structure is not reliable. The best equilibrium structure is: r_e(BF_cis) = 132.29 pm, r_e(BF_trans) = 131.29 pm, r_e(BO) = 134.48 pm, r_e(OH) = 95.74 pm, ∠_e(FBF) = 118.36°, ∠_e(F_cisBO) = 122.25°, and ∠_e(BOH) = 113.14°.     

Microwave and high resolution infrared spectra of vinyl chloride, ab initio anharmonic force field and equilibrium structure

The quadratic, cubic, and semi-diagonal quartic force field of vinyl chloride has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality. The spectroscopic constants derived from this force field are compared with the experimental values. To make this comparison more complete, the rotational constants of the lowest excited state, v₉ = 1 at 395 cm⁻¹ have been determined by microwave spectroscopy and the ν₁₂ band (around 618 cm⁻¹) has been investigated by high-resolution infrared Fourier transform spectroscopy. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-ζ quality and a core correlation correction. The experimental mass-dependent r_m structures are also determined and their accuracy is discussed. The recommended equilibrium geometry is: r (CC) = 1.3262(10), r (CCl) = 1.7263(10), r (CH_g) = 1.0784(10), r (CH_c) = 1.0795(10), r (CH_t) = 1.0797(10), ∠(CCCl) = 122.77(10)°, ∠(CCH_g) = 123.86(10)°, ∠(CCH_c) = 121.80(10)°, ∠(CCH_t) = 119.29(10)°.     

Ab initio anharmonic force field and equilibrium structure of vinyl fluoride and vinyl iodide

The quadratic, cubic and semi-diagonal quartic force field of vinyl fluoride and vinyl iodide have been calculated at the MP2 level of theory employing a basis set of triple-ζ quality including a relativistic pseudopotential on iodine. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality. Finally, the structure of different vinyl derivatives is compared.     

Ab initio anharmonic force field and equilibrium structure of vinyl bromide

The quadratic, cubic, and semi-diagonal quartic force field of vinyl bromide has been calculated at the MP2 level of theory employing a basis set of triple-ζ quality including a relativistic pseudopotential on bromine. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality and an offset correction. The experimental mass-dependent r_m structures are also determined and their accuracy is discussed.     

Pure rotational spectrum, ab initio anharmonic force field, and equilibrium structure of silyl chloride

The ground state rotational spectra of H₃Si³⁵Cl, H₃Si³⁷Cl, and D₃Si³⁵Cl have been measured from the microwave to the submillimeterwave ranges and accurate rotational parameters have been determined. For H₃Si³⁷Cl, they are in good agreement with the values obtained from the ground state combination differences. The quadratic, cubic, and semi-diagonal quartic force field has been calculated at the MP2 level of theory employing a basis set of polarized valence quadruple-zeta quality. This force field has been used to predict the spectroscopic constants. The calculated values are found to be in good agreement with the available experimental data. The equilibrium structure has been derived from the experimental ground state rotational constants and either the ab initio or the experimental rovibrational interaction parameters. These experimental and semi-experimental structures are in excellent agreement with the ab initio equilibrium geometry.     

Torsional barrier and equilibrium structure of ethyl cyanide

The quadratic, cubic and semi-diagonal quartic force field of ethyl cyanide has been calculated at the B3LYP level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. This structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quadruple-ζ quality and a core correlation correction. The empirical structures are also determined and their accuracy is discussed. The potential barrier V₃ hindering internal rotation of the methyl group has been calculated from 23 rotational transitions of CH₃CH₂C¹⁵N which were found split into doublets, giving V₃ = 3074(27) cal mol⁻¹.     

Ab initio anharmonic force field and equilibrium structure of the sulfonium ion

The semi-experimental equilibrium structure of the sulfonium ion, , has been obtained from the experimental ground-state rotational constants available for five isotopologues and the corresponding vibrational corrections computed at the CCSD(T)/cc-pwCVQZ level of theory. This geometry has been found in very good agreement with the pure ab initio equilibrium structure calculated at the CCSD(T) level of theory using a basis set of sextuple-zeta quality and including core correlation corrections. The anharmonic force field has been used for deriving spectroscopic properties: in particular, in addition to the vibrational corrections, the rotational parameters of the SH₂D⁺ isotopic species, not yet experimentally observed, have been predicted to a guessed good accuracy.     

Anharmonic force field and equilibrium structure of nitric acid

The quadratic, cubic and semi-diagonal quartic force field of nitric acid has been calculated at the CCSD(T) level of theory employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure has been derived from experimental ground state rotational constants and rovibrational interaction parameters calculated from the ab initio force field. It is found that the A and B semi-experimental equilibrium rotational constants of the ¹⁸O isotopologues (for which the rotation of principal axes is large) cannot be accurately reproduced. This problem is discussed and a remedy is proposed. Finally, the semi-experimental structure is in agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of at least quadruple-ζ quality and a core correlation correction, except for the long NO single bond for which the CCSD(T) value is too short due to inadequate treatment of electron correlation. The empirical structures are also determined and their accuracy is discussed. The best equilibrium structure is: r_e(NO_syn) = 1.209(1) Å, r_e(NO_anti) = 1.194(1) Å, r_e(NO) = 1.397(1) Å, r_e(OH) = 0.968(1) Å, ∠(ONO_syn) = 115.8(1)°, ∠(ONO_anti) = 114.2(1)° and ∠(NOH) = 102.2(1)°.     

Rotational spectra of isotopic species of silyl fluoride. Part II: Theoretical and semi-experimental equilibrium structure

The equilibrium structure of silyl fluoride, SiH₃F, has been reinvestigated using both theoretical and experimental data. With respect to the former, quantum-chemical calculations at the coupled-cluster level have been employed together with extrapolation to the basis set limit, consideration of higher excitations in the cluster operator, and inclusion of core correlation as well as relativistic corrections (r(Si-F) = 1.5911 Å, r(Si-H) = 1.4695 Å, and ∠FSiH = 108.30°). A semi-experimental equilibrium structure has been determined based on the available rotational constants for the various isotopic species of silyl fluoride (²⁸SiH₃F, ²⁸SiD₃F, ²⁹SiH₃F, ²⁹SiD₃F, ³⁰SiH₃F, ³⁰SiD₃F, ²⁸SiH₂DF, and ²⁸SiHD₂F) together with computed vibrational corrections to the rotational constants (r(Si-F) = 1.59048(6) Å, r(Si-H) = 1.46948(9) Å, and ∠FSiH = 108.304(9)°).     

Experimental,semi-experimental and ab initio equilibrium structures

The determination of equilibrium structures of molecules by spectroscopic methods or by quantum mechanical calculations is reviewed. The following structures are described in detail: experimental equilibrium structures, empirical structures, semi-experimental structures and ab initio structures. The approximations made by the different methods are discussed and their accuracies are compared.     

Fourier transform infrared spectroscopy of the 2ν3 overtone band of different ICN isotopomers: an improved evaluation of the anharmonic force field of cyanogen iodide

The weak 2ν₃ overtone band of the three isotopomers of cyanogen iodide, I¹²C¹⁴N, I¹³C¹⁴N, and I¹²C¹⁵N, has been recorded in the range from 4200 to 4400 cm⁻¹ with a resolution of 0.02 cm⁻¹ using a Fourier transform infrared spectrometer. The following band origins have been determined from the analysis of the spectra: ν₀ (I¹²C¹⁴N)=4332.8368 cm⁻¹, ν₀ (I¹³C¹⁴N)=4235.7355 cm⁻¹, and ν₀ (I¹²C¹⁵N)=4274.2851 cm⁻¹. This allowed us to achieve complete knowledge of the energies for all levels of ICN corresponding to double vibrational excitation. An improved evaluation of the quartic force field of cyanogen iodide has been performed using the new data obtained together with those already known from previous works.     

Submillimeterwave spectrum of CH2PH and equilibrium structures of CH2PH and CH2NH

The rotational spectrum of phosphaethene (CH₂PH) was reinvestigated. One hundred and nineteen new lines were measured in the submillimeter range from 500 to 650 GHz. The determination of the centrifugal distortion constants is significantly improved. As the molecule is close to symmetric prolate top, both reduction A and S were compared. The equilibrium structure has been derived from experimental ground state rotational constants and ab initio rovibrational interaction parameters. This semi-experimental structure is in excellent agreement with the ab initio structure calculated at the CCSD(T) level of theory using a basis set of quintuple-zeta quality and a core correlation correction. The structure of CH₂PH was compared to that of CH₂NH which was also determined for this goal. It is found that the semi-experimental structure of CH₂NH is less accurate than the ab initio structure. It is also found that the methylene group is much more asymmetric in CH₂NH than in CH₂PH.     

Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

The Born-Oppenheimer (BO) equilibrium molecular structure () of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure () has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The and structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C_m-O) = 1.434 Å, r(O-C_c) = 1.335 Å, r(C_m-H_s) = 1.083 Å, r(C_m-H_a) = 1.087 Å, r(C_c-H) = 1.093 Å, r(CO) = 1.201 Å, ∠(COC) = 114.4°, ∠(CCH_s) = 105.6°, ∠(CCH_a) = 110.2°, ∠(OCH) = 109.6°, ∠(OCO) = 125.5°, and τ(H_aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.     

Electronic structure and half-metallicity of the new Heusler alloys PtZrTiAl,PdZrTiAl and Pt0.5Pd0.5ZrTiAl

The electronic structure and magnetic properties of the PtZrTiAl, PdZrTiAl and Pt_0.5Pd_0.5ZrTiAl Heusler alloys were investigated using the full-potential linearized augmented plane wave (FPLAPW) within the generalized gradient approximation (GGA). For the PtZrTiAl, and PdZrTiAl alloys, the results showed that these Heusler alloys were stable in the Type I structure. The (Pt, Pd)ZrTiAl Heusler alloys are found to exhibit half-metallic ferromagnetism for both the Type I and Type II structure. The total magnetic moments of the PtZrTiAl and PdZrTiAl alloys were obtained to be 3 μ_B per formula unit, which are in agreement with the Slater-Pauling rule m_tot = (Nv ? 18). The half-metalliciy characteristic exists in the relatively wide ranges of 6.06–6.78 Å, and 6.13–6.73 Å for the PtZrTiAl and PdZrTiAl alloys, respectively. To complete the fundamental characteristics of these alloys, Pt_0.5Pd_0.5ZrTiAl is predicted to be a half-metallic ferromagnet with an energy gap of 0.90 eV in the minority spin and a complete spin polarization at the Fermi level. These new Heusler alloys may become ideal candidate material for future spintronic applications.     

Ab initio study of electronic structure and magnetic properties of copper (II) terephthalate

The first principles within the full potential linearized augmented plane wave (FP-LAPW) method was applied to study the compound of Cutp(OH₂)₂. The density of states, the electronic band structure and the spin magnetic moment are calculated. The calculations reveal that the compound has a ferromagnetic interaction arising from the bridging water molecule. The spin magnetic moment 1.0μ_B per molecule mainly comes from the Cu ion with little contribution from O, C anion.     

First-principles study of the electronic structure and magnetism of SrFe0.5Ru0.5O2

We study the electronic structures and magnetism of SrFe_0.5Ru_0.5O₂ by first-principles calculations in the framework of density functional theory (DFT) with generalized gradient approximation plus on site repulsion (GGA+U). The DFT calculations were carried out with ten kinds of Fe-site doping form. Calculations show that the d-orbital electronic configurations of Fe²⁺ and Ru²⁺ ions are (d_z²)²(d_yzd_xz)²(d_xy)²(d_x²_−y²)¹ and (d_z²)²(d_yzd_xz)³(d_xy)¹(d_x²_−y²) , respectively, which are independent of the doping form. The degenerated (d_xzd_yz) orbitals of Ru²⁺ ions are occupied by three electrons, so it gives rise to the Jahn–Teller distortion. The calculated magnetic moments of Fe²⁺ and Ru²⁺ ions are 3.7 μ_B and 1.6 μ_B, respectively. The exchange parameters including nearest neighbor (NN) ions and next nearest neighbor (NNN) ions are calculated by using Heisenberg model and the magnetic frustration in the ordered structure is explained by the competition of the exchange parameters. We also study the external pressure effect on the compound. A pressure-induced orthorhombic to tetragonal structure transition accompanied by an insulator to half-metal transition and an antiferromagnetic (or spin glass) to ferromagnetic state transition is observed.     

Single crystal growth,electronic structure and optical properties of Cs2HgBr4

We report on successful synthesis of high-quality single crystal of cesium mercury tetrabromide, Cs₂HgBr₄, by using the vertical Bridgman–Stockbarger method as well as on studies of its electronic structure. For the Cs₂HgBr₄ crystal, we have recorded X-ray photoelectron spectra for both pristine and Ar⁺ ion-bombarded surfaces. Our data indicate that the Cs₂HgBr₄ single crystal surface is rather sensitive with respect to Ar⁺ ion-bombardment. In particular, such a treatment of the Cs₂HgBr₄ single crystal surface alters its elemental stoichiometry. To explore peculiarities of the energy distribution of total and partial densities of states within the valence band and the conduction band of Cs₂HgBr₄, we have made band-structure calculations based on density functional theory (DFT) employing the augmented plane wave+local orbitals (APW+lo) method as incorporated in the WIEN2k package. The APW+lo calculations allow for concluding that the Br 4p states make the major contributions in the upper portion of the valence band, while its lower portion is dominated by contributors of the Hg 5d and Cs 5p states. Further, the main contributors to the bottom of the conduction band of Cs₂HgBr₄ are the unoccupied Br p and Hg s states. In addition, main optical characteristics of Cs₂HgBr₄ such as dispersion of the absorption coefficient, real and imaginary parts of dielectric function, electron energy-loss spectrum, refractive index, extinction coefficient and optical reflectivity have been explored from the first-principles band-structure calculations.     

High resolution infrared spectroscopy of [1.1.1]propellane

The infrared spectrum of [1.1.1]propellane has been recorded at high resolution (0.002 cm⁻¹) with individual rovibrational lines resolved for the first time. This initial report presents the ground state constants for this molecule determined from the analysis of five of the eight infrared-allowed fundamentals ν₉(e′), ν₁₀(e′), ν₁₂(e′), , as well as of several combination bands. In nearly all cases it was found that the upper states of the transitions exhibit some degree of perturbation but, by use of the combination difference method, the assigned frequencies provided over 4000 consistent ground state difference values. Analysis of these gave for the parameters of the ground state the following values, in cm⁻¹: B₀ = 0.28755833(14), D_J = 1.1313(5) × 10⁻⁷, D_JK = −1.2633(7) × 10⁻⁷, H_J = 0.72(4) × 10⁻¹³, H_JK = −2.24(13) × 10⁻¹³, and H_KJ = 2.25(15) × 10⁻¹³, where the numbers in parentheses indicate twice the uncertainties in the last quoted digit(s) of the parameters. Gaussian ab initio calculations, especially with the computed anharmonic corrections to some of the spectroscopic parameters, assisted in the assignments of the bands and also provided information on the electron distribution in the bridge-head carbon-carbon bond.