Electronic structure, spectroscopic properties, and state ordering of the isoelectronic diatomic molecules scandium oxide (ScO), titanium nitride (TiN), and vanadium carbide (VC)

Abstract

Local density functional computations, which take into account electron exchange-correlation and employ large one-particle Gaussian basis sets, are used to study the electronic structure and bonding of the of ScO, TiN, and VC low-lying states. While both ScO and TiN have 21+ ground states, arising from the 9af37rX23?r,2 electronic configuration, the VC diatomic is predicted to have a 2A ground state. The VC 2A ground state (8~~3~,~3?r,216,t) is the same as that suggested from EPR matrix-isolation experiments. The spectroscopic parameters ue, WeXe, Be, a,, and p and its derivatives are also computed for the three lowest 2Z+, ZA, and 211 states,

Electronic structures of 3d‐metal mononitrides

“…18 Our calculated bond distances (from 1.546 Å at B3PW91 to 1.583 Å at BLYP) are in agreement with the experimental value 1.582 Å and previous theoretical studies. 17,18,24,25 The calculated vibrational frequencies from different functionals are also reasonable compared with both experimental data 4,15 and previous theoretical studies. 17,18,24,25 For the dissociation energy, B3PW91 (4.92 eV) has the best performance in reproducing the experimental data 4.9 eV.…”

“…17,18,24,25 The calculated vibrational frequencies from different functionals are also reasonable compared with both experimental data 4,15 and previous theoretical studies. 17,18,24,25 For the dissociation energy, B3PW91 (4.92 eV) has the best performance in reproducing the experimental data 4.9 eV. 2 20 Other functionals either overestimate (B3PW91, BLYP, BPW91) or underestimate (BHLYP) those previous theoretical data.…”

“…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. 26 For the positive ions, theoretical studies are rare.…”

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

“…In the interim ab initio predictions for the electronic and geometric structure of TiN in its ground and low-lying excited states have been reported (9,10). In addition, the relative energy ordering and the |⌳S⌺J⍀͘ composition of the low-lying states of TiO arising from the Ti We report here on the submillimeter-wave spectra of TiO(X 3 ⌬) and TiN(X 2 ⌺ ϩ ) in the 220 -460 GHz and the PPMODR spectroscopic measurement of two lowest frequency rotational transitions of TiO(X 3 ⌬ 1 ).…”

Theoretical study of electronic structure of rhodium mononitride and interpretation of experimental spectra

“…Decades of research have provided plenty of information about the bonding of transition metal nitrides such as YN, [8,9] TcN, [10] RuN, [11][12][13] ReN, [14] and TiN. [15][16][17] However, the subject of this study, the RhN molecule, is not well understood as compared to the aforementioned metal-nitride species. Until 1997, Shim et al first presented the nature of the chemical bond and electronic structure of RhN by the multiconfiguration self-consistent field (MCSCF) and the multireference configuration interaction (MRCI) methods.…”