The permanent dipole moment of TiN and the nuclear magnetic hyperfine structure in its X 2Σ+ and A 2Π electronic states

Abstract

The permanent electric dipole moments and magnetic hyperfine interactions of ruthenium mononitride, RuNThe permanent dipole moment of TiN in its X 2l; + and A 2l; states has been determined from the complete resolution of the first-and second-order Stark splitting of the Q21 ( 1. 5) + R2 (0.5) line of the (0,0) band of the A 2II_X 2l; + system. Values of 3.56 ± 0.05 D (20-) and 4.63 ± 0.04 D (20-) have been derived for the X and A states respectively, from least-squares fits to plots of Stark splitting vs electric field strength. Electric fields up to 12 kV /cm have been employed avoiding voltage breakdown. The zero-field spectrum shows resolution of the nuclear magnetic hyperfine structure of the 47 TiN and 49 TiN isotopes. This hyperfine structure is that of the ground X 2l; + state only and is shown to follow closely the coupling case bps. The value ofthe Fermi contact parameter is -570 MHz which implies a 4s occupation of the 90-molecular orbital (MO) of 72 %. The results are compared with calculated and available experimental values for early first-row transition metal oxides and nitrides.7012

The Pure Rotational Spectra of TiO(X3Δ) and TiN(X2Σ+)

“…A supersonic molecular beam of TiO was generated by skimming the output from a laser ablation/reaction source (1,14). A mixture of ϳ5% O 2 in Ar was coexpanded with the 355 nm Nd:YAG vaporization products of a solid titanium rod.…”

“…The eigenvalues were obtained from numerical diagonalization of the case a ␤J representation of the operator of Eq. [1]. The data was reduced using weighted nonlinear least squares fitting program.…”

“…First, the limited number of valence electrons makes these simple titanium molecules excellent systems for a detailed analysis of transition metal bonding. The most insightful bonding information is derived from the analysis of the fine and hyperfine structure exhibited in their high-resolution spectrum (1)(2)(3). Secondly, titanium compounds are the source of optical spectral features of stars and may be present in circumstellar envelopes.…”

Electronic structures of 3d‐metal mononitrides

“…1 For 3d-metal mononitrides, experimental studies were available only for the neutral species. These include mass-spectrometric investigation on ScN, 2 TiN, 2 and VN; 2 near-infrared electronic emission spectra on ScN; 3 electronic spectra on TiN 4,5 and VN; 6 Stark spectra on TiN; 7 laser spectroscopy on TiN; 8 laser-induced fluorescence on VN 9,10 and CrN; 10,11 laser ablation and matrix infrared techniques on VN, 12 CrN, 12 MnN, 12 FeN, 13 CoN, 14 NiN, 14 and MN (MASc, Ti, V, Cr, Mn, Fe, Co, Ni). 15 Theoretical studies on the neutral species include MRCI (multireference configuration interaction) method on ScN, 16 TiN, 17,18 VN, 18,19 CrN, 18,20 FeN, 21 and NiN; 21 complete active space self-consistent field (CASSCF) on FeN; 20 CIPSI (configuration interaction by perturbation of a multiconfiguration wave function selected iteratively) method on ScN 22 and CuN; 23 CCSD(T) (coupled cluster singles doubles noniterative triples) on MN (MASc, Ti, V, Cr); 24 LDA-LCAO (local density functional linear combination of atomic orbitals) on TiN; 25 DFT (density functional theory) study with B3LYP (explanation see the second part) method on VN, 12 CrN, 12 MnN, 12 and FeN; 13 DFT 14,15 and MRSDCIϩQ (multireference single and double excitation configuration interaction with Davidson-type correction), as well as MRCPA (multireference coupled pair approximation) on CoN.…”

The Electric Dipole Moment of the B1Π State of ZrO

“…The dipole moment is one of the most important results from calculations of the electronic structure using ab initio methods. It has also been suggested that dipole moments should be used to calibrate ab initio calculations (8,9).…”