Theoretical analysis of equilibrium geometries and barriers of rotation in molecules H2X2, with X=O, S, Se, and Te

Block, R.; Jansen, L.

doi:10.1063/1.448231

Cited by 36 publications

(7 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, valence bond studies have shown that delocalization is necessary for reproducing torsion barriers at the staggered conformations of N 2 H 4 and H 2 O 2 , [9] and studies of basis set dependence with conventional molecular orbitals have found that torsion barriers are sensitive to the inclusion of polarization and diffuse function. [7,10] These observations agree with our conclusions to the extent that extended orbitals enhance the orbital overlap that is required for the exchange integrals.…”

Section: Discussionsupporting

confidence: 91%

Bending the Curve: Molecular Manifestations of Electron Antisymmetry

Herzfeld

Song

et al. 2021

ChemistryOpen

View full text Add to dashboard Cite

As very light fermions, electrons are governed by antisymmetric wave functions that lead to exchange integrals in the evaluation of the energy. Here we use the localized representation of orbitals to decompose the electronic energy in a fashion that isolates the enigmatic exchange contributions and characterizes their distinctive control over electron distributions. The key to this completely general analysis is considering the electrons in groups of three, drawing attention to the curvatures of pair potentials, rather than just their amplitudes and slopes. We show that a positive curvature at short distances is essential for the mutual distancing of electrons and a negative curvature at longer distances is essential to account for the influence of lone pairs on bond torsion. Neither curvature is available in the absence of the exchange contributions. Thus, although exchange energies are much shorter range than Coulomb energies, their influence on molecular geometry is profound and readily understood.

show abstract

Section: Discussionsupporting

confidence: 91%

Bending the Curve: Molecular Manifestations of Electron Antisymmetry

Herzfeld

Song

et al. 2021

ChemistryOpen

View full text Add to dashboard Cite

show abstract

“…The Te-Te-C (or TeTe-H) bond angle is ϳ97Њ (ϳ94Њ for H 2 Te 2 ) for the equilibrium structures and acquires some additional p character as the angle approaches the trans configuration. The only previous ab initio calculations [6,7] either did not involve full optimization of all of the coordinates or used a less sophisticated model, and they only report on the H 2 Te 2 molecule. The parameters reported in the most recent and oft-cited study [7] include Te-Te and Te-H bond distances of 2.73 and 1.67 Å , respectively, and Te-Te-H and torsional angles of 72Њ and 76Њ.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Calculations of the Rotational Barriers in H2Te2 and (CH3)2Te2

BelBruno

1997

Heteroat. Chem.

View full text Add to dashboard Cite

The heights of the rotational barriers of the ditelluride bridge in H2Te2 and (CH3)2Te2 have been calculated at the Hartree–Fock level with the 3‐21G basis set. The minima in the rotational potential energy functions occur at torsional angles of 87.58° and 89.32°, respectively. The barriers were determined by complete geometry optimization at each point along the potential surface. In addition, preliminary results on the stability of H2Te2 are reported. The molecule is found to be stable with respect to dissociation into H2Te + Te or H2 + Te2. © 1997 John Wiley & Sons, Inc. Heteroatom Chem 8: 199–202, 1997.

show abstract

“…The equilibrium values for the torsional angle were determined to be nearly perpendicular, 89.32Њ for (CH 3 ) 2 Te 2 and 87.58Њ for H 2 Te 2 . The parameters reported in the most recent and oft-cited study [7] include Te-Te and Te-H bond distances of 2.73 and 1.67 Å , respectively, and Te-Te-H and torsional angles of 72Њ and 76Њ. The Te-Te-C (or Te-Te-H) bond angle is ϳ97Њ (ϳ94Њ for H 2 Te 2 ) for the equilibrium structures and acquires some additional p character as the angle approaches the trans configuration.…”

Section: Resultsmentioning

confidence: 99%

Ab Initio Calculations of the Rotational Barriers in H2Te2 and (CH3)2Te2

BelBruno

1997

Heteroatom Chem.

View full text Add to dashboard Cite

The heights of the rotational barriers of the ditelluride bridge in H 2 Te 2 and (CH 3 ) 2 Te 2 have been calculated at the Hartree-Fock level with the 3-21G basis set. The minima in the rotational potential energy functions occur at torsional angles of 87.58Њ and 89.32Њ, respectively. The barriers were determined by complete geometry optimization at each point along the potential surface. In addition, preliminary results on the stability of H 2 Te 2 are reported. The molecule is found to be stable with respect to dissociation into H 2 Te ‫ם‬ Te or H 2

show abstract

Theoretical analysis of equilibrium geometries and barriers of rotation in molecules H2X2, with X=O, S, Se, and Te

Abstract: Removal of the discontinuities of the trial function in the computation of the electronic structure of molecules by the intersecting spheres model: Evaluation of the equilibrium geometry of N2 and H2O

Cited by 36 publications

References 51 publications

Bending the Curve: Molecular Manifestations of Electron Antisymmetry

Bending the Curve: Molecular Manifestations of Electron Antisymmetry

Ab Initio Calculations of the Rotational Barriers in H2Te2 and (CH3)2Te2

Ab Initio Calculations of the Rotational Barriers in H2Te2 and (CH3)2Te2

Contact Info

Product

Resources

About