Electronic structure and rovibrational properties of ZnOH in the $\tilde{X}\; ^{2}A^\prime$X̃2A′ electronic state: A computational molecular spectroscopy study

Abstract

The three-dimensional ground-state potential energy surface of ZnOH has been calculated ab initio at the MR-SDCI+Q_DK3/[QZP ANO-RCC (Zn, O, H)] level of theory and used as basis for a study of the rovibrational properties carried out by means of the program MORBID (Morse Oscillator Rigid Bender Internal Dynamics). The electronic ground state is (2)A' (correlating with (2)Σ(+) at the linear configuration). The equilibrium structure has r(e)(Zn-O) = 1.8028 Å, r(e)(O-H) = 0.9606 Å, and ∠e(Zn-O-H) = 114.9°. The Zn-O bond is essentially ionic, with appreciable covalency. The bonding character is compared with those of FeOH (quasi-linear) and CsOH (linear). The rovibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are ⟨r(Zn-O)⟩0 = 1.8078 Å, ⟨r(O-H)⟩0 = 0.9778 Å, and ⟨∠(Zn-O-H)⟩0 = 117°. The Yamada-Winnewisser quasi-linearity parameter is found to be γ0 = 0.84, which is close to 1.0 as expected for a bent molecule. Since no experimental rovibrational spectrum has been reported thus far, this spectrum has been simulated from the ab initio potential energy and dipole moment surfaces. The amphoteric character of ZnOH is also discussed.

Study of HgOH to Assess Its Suitability for Electron Electric Dipole Moment Searches

“…We followed the procedure outlined in the previous section, and found that the molecule is indeed bent in its ground electronic state ( 2 A state), unlike in the case of YbOH [30]. Although one may expect a metal-hydroxide molecule to be linear on grounds of the ionic nature of its bonding, a bent structure for HgOH indicates that the bond may possess a hint of covalent nature too, similar to the case of ZnOH [48,49]. We determined the optimized R Hg−O to be 2.2294 Å and R O−H to be 0.9633 Å, with the HgOH bond angle (θ Hg−O−H ) being 104.83 • .…”

Ro-vibrational properties of FeCO in the X̃3Σ- and Hirano1, Nagashima2 2015Journal of Molecular SpectroscopySelf Cite19020View full textAdd to dashboardCite

“…For the other cases including quasi-linear (c 0 % 0) and bent (c 0 % 1) molecules, the c 0 -values reported in our previous studies are compiled in Ref. [56] as Table X therein. If the fundamental and overtone bending transitions of a molecule have been observed experimentally and analyzed, the Yamada-Winnewisser quasi-linearity parameter can easily be derived from the observed vibrational energy spacings.…”

“…To shed new light on this long-standing problem, we have proposed to calculate ro-vibrationally averaged bond lengths and angle as expectation values over the relevant ro-vibrational wavefunctions. We have applied this method to several three-atom molecules [26,27,29,31,33,[54][55][56] and were able to obtain reasonable ro-vibrationally averaged structures. We found that in many cases, the experimentally derived bond lengths for the lighter atom pair (C-N, N-C, or O-H) in the molecule are too short in comparison with the calculated expectation values.…”

“…These Table 3 The vibrational energy spacings, Eðv1; v '2 2 ; v3; N min ¼ '2Þ À Eð0; 0 0 ; 0; 0Þ (in cm À1 ), for 56 Fe 12 C 16 O in the electronic statesX 3 R À andã 5 R À . a [12].…”

“…Effective rotational constants B eff are given in Table 4 for 56 Fe 12 C 16 O in theX 3 R À andã 5 R À electronic states. These Table 3 The vibrational energy spacings, Eðv1; v '2 2 ; v3; N min ¼ '2Þ À Eð0; 0 0 ; 0; 0Þ (in cm À1 ), for 56 Fe 12 C 16 O in the electronic statesX 3 R À andã 5 R À .…”