### Abstract

The objective of this work is to propose a way to calculate approximate transition state geometries that can then be used as initial guesses in ab initio calculations. Transition state geometries are calculated for 26 hydrogen transfer reactions and 6 methyl transfer reactions at the MP2/6-31G* and MP2/6-311 + +G(d,p) levels. Selected cases are also done at other levels including CCSD(T)/6-311 + + G(d,p). The transition state geometry obeys an equation which arises from an extension of the Marcus equation proposed by Blowers and Masel [8]: r^{t}_{B} + r^{t}_{F}/r_{B,equ} + r_{F,equ} = 1.25 ± 0.04 In this equation, r_{B,equ} is the equilibrium bond length for the bond that breaks during the reaction, r_{F,equ} is the equilibrium bond length for the new bond which forms. r^{t}_{B} and r^{t}_{F} are the bond lengths at the saddle point in the potential energy surface. r^{t}_{B} and r^{t}_{F} are found to obey (equation presented) with an average error of 0.04 Å. In the last two equations above, ΔU is the heat of reaction. E^{0}_{A} is the intrinsic barrier, and C_{A} is a constant that comes from the model of Blowers and Masel [8]. It is proposed that the above three equations are useful in generating initial guesses for transition state geometries in ab initio calculations. In the cases that were tried, rapid convergence was found when these guesses were used.

Original language | English (US) |
---|---|

Pages (from-to) | 46-54 |

Number of pages | 9 |

Journal | Theoretical Chemistry Accounts |

Volume | 105 |

Issue number | 1 |

State | Published - Nov 2000 |

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### Keywords

- ab initio
- Transition state

### ASJC Scopus subject areas

- Physical and Theoretical Chemistry

### Cite this

**Extensions of the Marcus equation for the prediction of approximate transition state geometries in hydrogen transfer and methyl transfer reactions.** / Blowers, Paul; Masel, Richard I.

Research output: Contribution to journal › Article

*Theoretical Chemistry Accounts*, vol. 105, no. 1, pp. 46-54.

}

TY - JOUR

T1 - Extensions of the Marcus equation for the prediction of approximate transition state geometries in hydrogen transfer and methyl transfer reactions

AU - Blowers, Paul

AU - Masel, Richard I.

PY - 2000/11

Y1 - 2000/11

N2 - The objective of this work is to propose a way to calculate approximate transition state geometries that can then be used as initial guesses in ab initio calculations. Transition state geometries are calculated for 26 hydrogen transfer reactions and 6 methyl transfer reactions at the MP2/6-31G* and MP2/6-311 + +G(d,p) levels. Selected cases are also done at other levels including CCSD(T)/6-311 + + G(d,p). The transition state geometry obeys an equation which arises from an extension of the Marcus equation proposed by Blowers and Masel [8]: rtB + rtF/rB,equ + rF,equ = 1.25 ± 0.04 In this equation, rB,equ is the equilibrium bond length for the bond that breaks during the reaction, rF,equ is the equilibrium bond length for the new bond which forms. rtB and rtF are the bond lengths at the saddle point in the potential energy surface. rtB and rtF are found to obey (equation presented) with an average error of 0.04 Å. In the last two equations above, ΔU is the heat of reaction. E0A is the intrinsic barrier, and CA is a constant that comes from the model of Blowers and Masel [8]. It is proposed that the above three equations are useful in generating initial guesses for transition state geometries in ab initio calculations. In the cases that were tried, rapid convergence was found when these guesses were used.

AB - The objective of this work is to propose a way to calculate approximate transition state geometries that can then be used as initial guesses in ab initio calculations. Transition state geometries are calculated for 26 hydrogen transfer reactions and 6 methyl transfer reactions at the MP2/6-31G* and MP2/6-311 + +G(d,p) levels. Selected cases are also done at other levels including CCSD(T)/6-311 + + G(d,p). The transition state geometry obeys an equation which arises from an extension of the Marcus equation proposed by Blowers and Masel [8]: rtB + rtF/rB,equ + rF,equ = 1.25 ± 0.04 In this equation, rB,equ is the equilibrium bond length for the bond that breaks during the reaction, rF,equ is the equilibrium bond length for the new bond which forms. rtB and rtF are the bond lengths at the saddle point in the potential energy surface. rtB and rtF are found to obey (equation presented) with an average error of 0.04 Å. In the last two equations above, ΔU is the heat of reaction. E0A is the intrinsic barrier, and CA is a constant that comes from the model of Blowers and Masel [8]. It is proposed that the above three equations are useful in generating initial guesses for transition state geometries in ab initio calculations. In the cases that were tried, rapid convergence was found when these guesses were used.

KW - ab initio

KW - Transition state

UR - http://www.scopus.com/inward/record.url?scp=0034310207&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034310207&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0034310207

VL - 105

SP - 46

EP - 54

JO - Theoretical Chemistry Accounts

JF - Theoretical Chemistry Accounts

SN - 1432-881X

IS - 1

ER -