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Development and application of a hybrid method involving interpolation and ab initio calculations for the determination of transition states
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10.1063/1.2992618
/content/aip/journal/jcp/129/17/10.1063/1.2992618
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/17/10.1063/1.2992618

Figures

Image of FIG. 1.
FIG. 1.

A flow sheet for the evolution step of the modified GSM. The orthogonal force , refers to the negative of the component of the gradient that is orthogonal to the reaction path. The criterion for using the interpolation scheme is if there are points within a confidence length .

Image of FIG. 2.
FIG. 2.

A flow sheet for a TS-finding strategy that uses a combined low level/high level of theory approach. A TS search using a high level of theory can be initiated directly from the converged low-level string. Otherwise, if the topology of the PES is correct, the low-level string can be further refined at a high level of theory.

Image of FIG. 3.
FIG. 3.

Contour plot of the Müller–Brown potential energy surface showing the three minima (A, B, C) and two saddle points, or TSs (TS1, TS2).

Image of FIG. 4.
FIG. 4.

Error in the estimate of the highest saddle point from the true saddle point (TS1) on the MB PES. Results are shown at 18 nodes for the GSM and modified GSM. The open circles represent points where an interpolation step was performed in the modified GSM.

Image of FIG. 5.
FIG. 5.

Final energy profile of the MEP for the MB PES using the GSM and the modified GSM for 18 nodes. The points in each curve are joined with a spline.

Image of FIG. 6.
FIG. 6.

Alanine dipeptide isomerization from species (reactant) to (product).

Image of FIG. 7.
FIG. 7.

Error in the estimate of the highest saddle point from the true saddle point for alanine dipeptide isomerization. Results are shown at 11 nodes for the GSM and modified-GSM. The open circles represent points where an interpolation step was performed in the modified GSM.

Image of FIG. 8.
FIG. 8.

Final energy profile of the MEP for alanine dipeptide isomerization using the GSM and the modified GSM for 11 nodes. The reaction path shown for the modified GSM is after single-point QM calculations have been performed on interpolated points that exist in the final string. The points in each curve are joined with a spline.

Image of FIG. 9.
FIG. 9.

H abstraction in methanol oxidation on .

Image of FIG. 10.
FIG. 10.

Error in the estimate of the highest saddle point from the true saddle point for H abstraction in methanol oxidation on . Results are shown at 11 nodes for the GSM and modified GSM. The open circles represent points where an interpolation step was performed in the modified GSM.

Image of FIG. 11.
FIG. 11.

Final energy profile of the MEP for H abstraction in methanol oxidation on using the GSM and the modified GSM for 11 nodes. The reaction path shown for the modified GSM is after single-point QM calculations have been performed on interpolated points that exist in the final string.

Image of FIG. 12.
FIG. 12.

C–H bond activation in toluene on a Rh complex coordinated with two CO species and three TFA solvent ligands.

Image of FIG. 13.
FIG. 13.

Error in the estimate of the highest saddle point from the true saddle point for C–H bond activation in toluene over Rh/TFA complex. The result shown is at 11 nodes for the modified GSM. The GSM is not shown because it was unable to converge. The open circles represent points where an interpolation step was performed in the modified GSM.

Image of FIG. 14.
FIG. 14.

Final energy profile of the MEP for C–H bond activation in toluene over Rh/TFA complex using the modified GSM for 11 nodes. The modified GSM was first used using HF/STO-3G, and then refined using B3LYP/6-31G/LANL2DZ. The points in each curve are joined with a spline.

Tables

Generic image for table
Table I.

Comparison of TS geometries from final string calculations for alanine dipeptide isomerization. The energies are relative to the reactant, .

Generic image for table
Table II.

Time required to determine the TS for alanine dipeptide isomerization.

Generic image for table
Table III.

Comparison of TS geometries from final string calculations for H abstraction in methanol oxidation on . The strings were grown using the functional/basis sets listed. All TS estimates were refined at .

Generic image for table
Table IV.

Time required to determine the TS for H transfer in .

Generic image for table
Table V.

Comparison of TS geometry using different functionals/basis sets for C–H bond activation in toluene on .

Generic image for table
Table VI.

Time required to determine the TS for C–H activation in toluene over .

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/content/aip/journal/jcp/129/17/10.1063/1.2992618
2008-11-06
2014-04-19
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Development and application of a hybrid method involving interpolation and ab initio calculations for the determination of transition states
http://aip.metastore.ingenta.com/content/aip/journal/jcp/129/17/10.1063/1.2992618
10.1063/1.2992618
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