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A quantum chemical study of : Intramolecular torsional mode and intermolecular interactions with rare gases
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10.1063/1.2994732
/content/aip/journal/jcp/129/16/10.1063/1.2994732
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/16/10.1063/1.2994732

Figures

Image of FIG. 1.
FIG. 1.

Variation of the energy profile of the molecule as a function of dihedral angles for different theory levels and basis sets. The experimental barriers (Ref. 30) are 2800(90) and for cis and trans configurations, respectively.

Image of FIG. 2.
FIG. 2.

Variation of the energy of the and molecules as a function of dihedral angles at MP2(FU)/aug-cc-pVTZ level. The trans barrier is higher for with respect to that (2003.0 vs ).

Image of FIG. 3.
FIG. 3.

Variation of dipole moment of the and molecules as a function of dihedral angles at CCSD(t)/aug-cc-pVDZ level. The experimental values in the equilibrium geometries are 1.17 and 1.57 D for and , respectively.

Image of FIG. 4.
FIG. 4.

Effects of basis set on dipole moment for at several theory levels. Best fit curves are drawn as an aid for the eye, using formula of the type of Eq. (1) in Ref. 31. The experimental value in the equilibrium geometry is 1.17 D for .

Image of FIG. 5.
FIG. 5.

Definition of the spherical coordinates of the vector , , specifying the position of the rare gas atom for equilibrium geometry. is the distance between the center of mass of the molecule and the rare gas atom, is the angle between and the axis and is the angle between axis and the projection of onto the plane.

Image of FIG. 6.
FIG. 6.

and interaction energies for the leading configurations as a function of the distance of the rare gas from the center of mass of the hydrogen persulfide molecule (see Ref. 18). Crosses indicate ab initio points (others lie outside of the drawings) and curves are from Rydberg fits, as described in the text.

Image of FIG. 7.
FIG. 7.

and interaction energies for the leading configurations as a function of the distance of the rare gas from the center of mass of the hydrogen persulfide molecule (see Ref. 18). Crosses indicate ab initio points (others lie outside of the drawings) and curves are from Rydberg fits, as described in the text.

Image of FIG. 8.
FIG. 8.

Rare interaction energies as a function of the distance of the rare gas from the center of mass of the hydrogen persulfide molecule, for the equilibrium geometry and the rare gas atom approaching from a direction given by and . Lower panel: Crosses indicate ab initio points (others lie outside of the drawing) and curves are from Rydberg fits, as described in the text. Upper panel: Curves indicate hyperspherical expansion representation as described in the text.

Image of FIG. 9.
FIG. 9.

Dependence on atom-molecule distance of some representative isotropic (continuous curves) and anisotropic (dashed curves) moments of the hyperspherical expansion for .

Image of FIG. 10.
FIG. 10.

Illustration of the potential energy surface for the interaction of Ar with , as angle varies in the plane (Ref. 18) in the equilibrium geometry and the angle is . The radial coordinate in this plane of the molecule. At the distance around from the center of mass of the molecule, the Ar atom is in a shallow well (around ) slightly deeper for (atom facing the spine of the book). The other rare gas behave similarly.

Image of FIG. 11.
FIG. 11.

View of the potential energy surface for the interaction of Ar with , as the torsional angle varies in the plane (see Ref. 18). The radial coordinate is this plane is the distance of the Ar atom from the center-of-mass of the molecule and the approach to the SS bond is and . Visible are the steep barriers of the cis and trans forms separating the two enantiomeric equilibrium geometries.

Tables

Generic image for table
Table I.

Geometries, energies, and dipole moments for the with different basis sets and theory levels.

Generic image for table
Table II.

Cis and trans barriers for the torsional mode for different basis sets and theory levels.

Generic image for table
Table III.

Cis and Trans geometric parameters for with different basis sets and theory levels.

Generic image for table
Table IV.

Well depths , and corresponding atom-molecule distance of the average isotropic expansion moment . Comparison with polarizability model, Ref. 44.

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/content/aip/journal/jcp/129/16/10.1063/1.2994732
2008-10-23
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A quantum chemical study of H2S2: Intramolecular torsional mode and intermolecular interactions with rare gases
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/16/10.1063/1.2994732
10.1063/1.2994732
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