Rotation–vibration energy cluster formation in XH2D and XHD2 molecules (X=Bi, P, and Sb)

A theoretical-spectroscopy, ab initio-based study of the electronic ground state of 121SbH3

“…This can be readily verified by inspecting Table 5. For the transition moments µ f i that couple the ground state with the stretching states (100) and (200) we obtain: |⟨100; E|µ|000; A 1 ⟩| 2|⟨100; A 1 |µ|000; A 1 ⟩| = 0.251386 0.291202 ≈ 0.86 (21) and |⟨200; E|µ|000; A 1 ⟩| 2|⟨200; A 1 |µ|000; A 1 ⟩| = 0.025799 0.033452 ≈ 0.77.…”

“…Also, TROVE has been used to predict and interpret the complicated torsional splittings of the HSOH molecule [18], to explain an intensity anomaly observed in this molecule [19,20] and to predict highly excited rotational energies in deuterated isotopologues of BiH 3 , SbH 3 , and AsH 3 [21]. The theoretical calculations of rotation-vibration energies and intensities are generally based on ab initio potential energy surfaces (PES) and dipole moment surfaces (DMS); in some instances we have refined the analytical representations of the PES in simultaneous least-squares fittings to experimentally derived vibrational energy spacings and ab initio data.…”

“…Our theoretical studies of these molecules have been generally aimed at providing predictions for laboratory spectroscopy with the hope of facilitating the experimental characterization of the energy cluster states. In particular, quite recently [21] we have carried out TROVE calculations for singly-and di-deuterated isotopologues of PH 3 , BiH 3 , and SbH 3 (together with some effectiverotational-Hamiltonian calculations for AsH 2 D and AsHD 2 ), demonstrating for the first time that some of these isotopologues have energy clusters.…”

Molecular Eigensolution Symmetry Analysis and Fine Structure

“…The RES was introduced about thirty years ago [8] to analyze spectral fine structure of high resolution spectral bands in molecules of high symmetry including PH 3 [9] XDH 3 and XD 2 H molecules [10], tetrahedral ( P 4 ) [11], tetrafluorides ( CF 4 and SiF 4 ) [12], hexafluorides ( SF 6 , Mo ( CO ) 6 and UF 6 ) [13–16], cubane ( C 8 H 8 ), and buckyball ( C 60 ) [15,16] and predicted major mixing of Herzberg rovibronic species. Recently RES have been extended to help understand the dynamics and spectra of fluxional rotors [17] or “floppy” molecules such as methyl-complexes [18] and vibrational overtones [2].…”

High resolution infrared study of SbHD2: The ground state and the Sb–H stretching bands ν1 and 2ν1

“…Furthermore, experimental ground state energies of PH 2 D, PHD 2 , AsH 2 D, and AsHD 2 have been used to estimate the reliability of the energy cluster formation in rotational states with J 6 70 as calculated by means of a variational approach [21].…”