Vibrational motion in the state of LiSH and LiSD

Khadri, F.; Zaidi, Ali; Lahmar, S.; Lakhdar, Z. Ben; Rosmus, P.; Hochlaf, M.

doi:10.1080/00268970701581465

Cited by 5 publications

(15 citation statements)

References 19 publications

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“…On the other hand, the active space formed by CAS(8,13) is almost optimum. For example, the optimized CAS(8,13)/6-311++G(d,p) structure (RLi-S = 4.0744 a0, RS-H = 2.5660 a0, and θ = 92.96°) compares well with the MRCI results from Khadri et al [5]. The older theoretical calculations reported by Pappas [7] considerably differ from the present findings.…”

Section: Calculated Properties Of the Singlet Ground Statesupporting

confidence: 76%

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Theoretical characterization of the LiSH potential energy surface

Silva

Furones²

2022

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Electronic structure calculations have been performed to characterize the potential energy surface of the LiSH. For such, molecular properties have been calculated using two different levels of theories: DFT/B3LYP and CASSCF. As results, the obtained equilibrium geometry at CAS(8,13)/VQZ level of theory is RLi-S = 4.0975 a0, RS-H = 2.5502 a0, and θ = 93.37°. The present vibrational harmonic frequencies are in good agreement with those previously reported in the literature. Our results show the overall endothermicity of the Li(²P) + SH(X²Π) → H(2S) + LiS(X²Π) to be about 0.508 eV without ZPE corrections at CAS(8,13)/VQZ. Besides, the role of the molecular singlet-triplet transitions, essential for the interpretation of the phosphorescence spectra, is discussed. Overall, the present findings reproduced well the experimental ones and, therefore, can be used as a benchmark for other theoretical and experimental studies.

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Section: Calculated Properties Of the Singlet Ground Statesupporting

confidence: 76%

“…The DFT B3LYP/6-311++G(d,p) calculations provide a ground geometry that differs by 0.01 a0 and 1.3° from the experimental RLi-S and θ. From this table, the worst results are identified for the DFT B3LYP/TZVP when compared with [4] and [5]. Similar geometries are shown for the B3LYP in the VTZ and VQZ basis sets.…”

Section: Methodsmentioning

confidence: 60%

Theoretical characterization of the LiSH potential energy surface

Silva

Furones²

2022

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“…Nevertheless, this approach is not justifiable for CuOH as the barrier to linearity is only ∼0.4 eV (∼3200 cm –1 ). This means that the molecule possesses a large amplitude motion around this coordinate as previously described for other MOH and MSH triatomics. ,− This leads to a double potential well with delocalized vibrational wave functions for the states above 3600 cm –1 . For such molecular systems, only a full treatment of the nuclear motions via a variational approach is appropriate.…”

Section: Resultssupporting

confidence: 54%

Copper–Chalcogen Bonds in Olfaction: Accurate ab Initio Characterization of CuSH and CuOH

et al. 2019

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From highly correlated ab initio methods at the CCSD(T) level, with and without the inclusion of scalar relativistic effects, accurate 3D potential energy surfaces (PESs) of CuSH and CuOH were generated in their electronic ground state. The PESs are incorporated into perturbative and variational treatments of nuclear motions. Using these approaches, we derived a set of accurate spectroscopic parameters and the pattern of the vibrational states of CuXH (X = O,S) up to 4000 cm −1 . The applied calculations at the CCSD(T)/aug-cc-pV5Z-DK level of theory are validated using several experimental highresolution spectroscopy data (including rotational spectroscopy) available in the literature. The optimized equilibrium geometries of CuSH and CuOH with bending angles of 93.9°a nd 110.2°, Cu−X bond lengths of 2.088 and 1.764 Å, and X−H bond lengths of 1.344 and 0.961 Å, respectively, accurately reproduce the experimental structures and clearly show the importance of the scalar relativistic effects. The anharmonic frequencies, ν 1 , ν 2 , and ν 3 , are computed at 3655.5, 746.3, and 623.3 cm −1 for CuOH and at 2572.9, 588.9, and 396.6 cm −1 for CuSH, respectively. Finally, the PESs are derived as anharmonic force fields for CuXH (X = O, S) that can be incorporated into large scale molecular dynamics simulations of Cu−X containing compounds. The results are discussed within the scope of available literature on the effects of substitution of oxygen by sulfur for putative molecular recognition mechanisms.

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“…It is worth noting that our spectroscopic constants (Rotational constants, harmonic wavenumbers, anharmonicity terms) were computed from the derivatives of the potentials at their respective minima. We estimate the accuracy of our rovibrational energies to be $10 cm À1 according to similar studies on metallic triatomic compounds [17][18][19].…”

Section: Electronic Structure Calculations Methodsmentioning

confidence: 99%

“…x 3 < m 3 ), which can be related here again to the flatness of this 3D-PES along this coordinate. Such a behaviour is frequently occurring for metallic bearing compounds [17,18]. Table 3 lists the rovibrational theoretical spectrum of l-MgOO þ ð e X 4 R À Þ up to $700 cm À1 above the zero point energy.…”

Section: Spectroscopy Of Mgo þmentioning

confidence: 98%