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Transition state-finding strategies for use with the growing string method
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10.1063/1.3156312
/content/aip/journal/jcp/130/24/10.1063/1.3156312
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/24/10.1063/1.3156312

Figures

Image of FIG. 1.
FIG. 1.

Three transition state (TS)-finding strategies for use with the modified-GSM. The three strategies are used for determining the TS joining reactant (A) and product (B).

Image of FIG. 2.
FIG. 2.

Alanine dipeptide isomerization from species (reactant) to (product) characterized by the rotation of the two dihedral angles and .

Image of FIG. 3.
FIG. 3.

H-abstraction in methanol oxidation on involving one of the three methoxy H atoms transferring to the vanadyl O atom.

Image of FIG. 4.
FIG. 4.

C–H bond activation in the oxidative carbonylation of toluene to -toluic acid on a Rh complex coordinated with two CO species and three TFA solvent ligands.

Image of FIG. 5.
FIG. 5.

Intramolecular rearrangement of cyclopropane to propylene. The optimized geometries of reactant, transition state, and product are shown along with the final string.

Image of FIG. 6.
FIG. 6.

The rearrangement of methylcyclopropane to form the stereoisomers 1-butene, cis-2-butene, trans-2-butene, and isobutene. The C atoms in the ring of methylcyclopropane are numbered.

Image of FIG. 7.
FIG. 7.

Bimolecular Diels–Alder reaction of 1,3-butadiene and ethylene to cyclohexene. The optimized geometries of reactant, transition state, and product are shown along with the final string. The two reactant species are located 3.0 Å apart. The transition state consists of the concerted motion of the two reactant species moving toward each other (step 1), the rotation of ethylene (step 2), and the formation of two weak C–C bonds (step 3).

Image of FIG. 8.
FIG. 8.

Comparison of the distribution of time spent on growth of the string, determination of the Hessian, and optimization of the transition state estimate for the original GSM, the modified-GSM, and the modified-GSM using the substring strategy. The calculated times in hours are shown for H-transfer in methanol oxidation on .

Tables

Generic image for table
Table I.

Time required to determine the TS for alanine dipeptide isomerization using different calculational methods and TS-finding strategies. All TS estimates were further optimized at to determine the final TS.

Generic image for table
Table II.

Comparison of the final TS geometries for alanine dipeptide isomerization using different calculational methods and TS-finding strategies. See Table I for the functional and basis sets used to grow the string. All TS estimates were refined at to determine the final TS. The energies of the optimized reactant, product, and TS structures were determined from single-point calculations at and zero-point corrected.

Generic image for table
Table III.

Time required to determine the TS for H-transfer in methanol oxidation on using different calculational methods and TS-finding strategies. All TS estimates were further optimized at to determine the final TS. The LANL2DZ basis set was used for V.

Generic image for table
Table IV.

Comparison of the final TS geometries for H-abstraction in methanol oxidation on using different calculational methods and TS-finding strategies. See Table III for the functional and basis sets used to grow the string. All TS estimates were refined at to determine the final TS. The energies of the optimized reactant, product, and TS structures were determined from single-point calculations at and zero-point corrected.

Generic image for table
Table V.

Time required to determine the TS for C–H bond activation in toluene on using different calculational methods and TS-finding strategies. All TS estimates were further optimized at to determine the final TS. The LANL2DZ basis set was used for Rh.

Generic image for table
Table VI.

Comparison of the final TS geometries for C–H bond activation in toluene on using different calculational methods and TS-finding strategies. See Table V for the functional and basis sets used to grow the string. All TS estimates were refined at to determine the final TS. The energies of the optimized reactant, product, and TS structures were determined from single-point calculations at and zero-point corrected.

Generic image for table
Table VII.

Comparison between experimental and theoretical values obtained in the present work for the energetics and kinetics of cyclopropane isomerization to propylene. The reaction enthalpy at standard state , activation energy , preexponential factor , and rate constant at 773 K are shown. The energies of the optimized reactant, product, and TS structures were determined from single-point calculations at and zero-point corrected.

Generic image for table
Table VIII.

Comparison between experimental and theoretical values obtained in the present work for , , and the relative reaction rates for the rearrangement of methylcyclopropane for each stereoisomer. The energies of the optimized reactant, product, and TS structures were determined from single-point calculations at and zero-point corrected. All energies are reported in units of kcal/mol.

Generic image for table
Table IX.

Comparison between experimental and theoretical values obtained in the present work for the energetics and kinetics of the Diels–Alder reaction of 1,3-butadiene and ethylene to cyclohexene. The reaction enthalpy at standard state , activation energy , and rate constant at 823 K are shown. The energies of the optimized reactant, product, and TS structures were determined from single-point calculations at and zero-point corrected.

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/content/aip/journal/jcp/130/24/10.1063/1.3156312
2009-06-26
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Transition state-finding strategies for use with the growing string method
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/24/10.1063/1.3156312
10.1063/1.3156312
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