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Combined-hyperbolic-inverse-power-representation of potential energy surfaces: A preliminary assessment for and
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10.1063/1.4788912
/content/aip/journal/jcp/138/5/10.1063/1.4788912
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/5/10.1063/1.4788912

Figures

Image of FIG. 1.
FIG. 1.

Potential energy curve for the electronic ground state of OH as obtained by fitting MRCI+Q/AVQZ energies with the EHFACE2U (dashed line) and CHIPR (solid line) formalisms. The errors for the latter are indicated in the bottom panel, while the short-range repulsive region is shown in the insert of the top panel.

Image of FIG. 2.
FIG. 2.

As in Figure 1 but for . For better visibility, the error bars referring to the highly repulsive points have been truncated but, as shown from the insert, the percent errors are still rather small.

Image of FIG. 3.
FIG. 3.

HH contracted basis from a fit to energies for equilateral triangular geometries of trihydrogen. Points were chosen from the range 0.8 ⩽ R/a0 ⩽ 6.0 or reproduction of the 10 pivotal ones (solid dots) democratically selected over the same range. The arrows indicate the distributed origins that have been optimally defined for each fit. Shown in gray is the fully optimized basis b8 suitably scaled by 0.5.

Image of FIG. 4.
FIG. 4.

Rmsd for 9477 points covering a uniformly dense region defined by 0.8 ⩽ R 1/a0 ⩽ 6.0 (similarly for R 2) and included angles , spaced by and , respectively. All fits were done with the basis b8.

Image of FIG. 5.
FIG. 5.

Lowest adiabatic potential energy surface for collinear geometries of as fitted to 9477 DMBE points with a polynomial expansion up to power 20 in the basis b8. See text.

Image of FIG. 6.
FIG. 6.

Fits to 9477 (top panel) and 420 (bottom) points for with a polynomial expansion up to power 20 in basis b8.

Image of FIG. 7.
FIG. 7.

O–H and O–O contracted basis as obtained from a fit to energies for 1D cuts along the PES keeping the angle fixed at the equilibrium value: in black for O–OH stretching, in gray for H–OO. For visibility, the optimized basis have been multiplied by suitable constant scaling factors.

Image of FIG. 8.
FIG. 8.

Contour plot for bond stretching in O–O–H fixed at its equilibrium included angle. Contours are equally spaced by , starting at .

Image of FIG. 9.
FIG. 9.

Contour plot for an O atom moving around OH fixed at its equilibrium geometry and lying along the X axis with the center of the bond fixed at the origin. Contours are equally spaced by , starting at . In dash are contours equally spaced by , starting at .

Image of FIG. 10.
FIG. 10.

Isotropic components of the O–OH and interactions as predicted with the diatomic molecule fixed at its equilibrium geometry (reference energy taken at asymptote).

Tables

Generic image for table
Table I.

Some non-zero coefficients employed in the expansion of Eq. (3) .

Generic image for table
Table II.

CHIPR curves a for ground state OH and O2.

Generic image for table
Table III.

H–H contracted basis a for H3.

Generic image for table
Table IV.

Saddle point attributes a for the exchange reaction.

Generic image for table
Table V.

O–H and O–O contracted basis a for HO2.

Generic image for table
Table VI.

Accumulated unweighted rmsd (in ) of the CHIPR fits a to DMBE IV for ground-state HO2.

Generic image for table
Table VII.

Attributes of major stationary points of HO2 potential energy surface. a Unless indicated otherwise, energies are relative to the covalent minimum.

Generic image for table
Table VIII.

A summary of rate constants a for the reaction. b

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/content/aip/journal/jcp/138/5/10.1063/1.4788912
2013-02-07
2014-04-18
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Combined-hyperbolic-inverse-power-representation of potential energy surfaces: A preliminary assessment for H3 and HO2
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/5/10.1063/1.4788912
10.1063/1.4788912
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