Transition structure modeling by intersecting potential energy surfaces

A previously proposed method of modeling force field transition structures as the lowest energy structure on the seam of two intersecting potential energy surfaces is improved with respect to the force field expression and the efficiency of the optimization algorithm. Comparison with ab initio and experimental results show that the force field method may have the potential of achieving almost quantitative results. It appears that the results from transition state modeling are currently limited by the accuracy of the underlying force field. © 1994 by John Wiley & Sons, Inc.

[1]  S. Shaik,et al.  Is the avoided crossing state a good approximation for the transition state of a chemical reaction? An analysis of Menschutkin and ionic SN2 reactions , 1994 .

[2]  Kendall N. Houk,et al.  TRANSITION-STATE MODELING WITH EMPIRICAL FORCE FIELDS , 1993 .

[3]  D. Yarkony,et al.  On the intersection of two potential energy surfaces of the same symmetry. Systematic characterization using a Lagrange multiplier constrained procedure , 1993 .

[4]  D. Yarkony,et al.  Systematic determination of intersections of potential energy surfaces using a Lagrange multiplier constrained procedure , 1993 .

[5]  Frank Jensen,et al.  A theoretical study of steric effects in SN2 reactions , 1992 .

[6]  K. Houk,et al.  Empirical force-field models for the transition states of intramolecular diels-alder reactions based upon ab initio transition structures , 1992 .

[7]  D. Yarkony.  Theoretical studies of spin-forbidden radiationless decay in polyatomic systems : insights from recently developed computational methods , 1992 .

[8]  A. Peyman,et al.  Modeling a reaction path by molecular mechanics: Dimerization of carbon free radicals , 1992 .

[9]  H. W. Schranz,et al.  Comparisons of statistical and nonstatistical behavior for bond fission reactions in 1,2‐difluoroethane, disilane, and the 2‐chloroethyl radical , 1991 .

[10]  K. Houk,et al.  MM2 model for the intramolecular additions of acyl-substituted radicals to alkenes , 1991 .

[11]  B. Trost,et al.  Theoretical studies of stereoselectivities of nucleophilic 1,2-additions to cyclohexenones. Transition structures and force-field models for metal hydride and keteniminate additions to ketones , 1991 .

[12]  Michel Dupuis,et al.  On the determination of the minimum on the crossing seam of two potential energy surfaces , 1991 .

[13]  L. Raff,et al.  Trajectory study of Si4 formation and decay and of exchange and abstraction reactions in Si+Si3 collisions , 1990 .

[14]  F. Menger,et al.  Origin of high predictive capabilities in transition-state modeling , 1990 .

[15]  W. Hase,et al.  A Model Analytic Potential Energy Function for Formyl Radical Decomposition , 1990 .

[16]  S. Shaik,et al.  The quantum mechanical resonance energy of transition states: an indicator of transition state geometry and electronic structure , 1990 .

[17]  P. Hiberty,et al.  Quantitative valence bond computations of curve-crossing diagrams for model atom exchange reactions , 1990 .

[18]  W. Hase,et al.  Complete multidimensional analytic potential energy surface for chloride + chloroform SN2 nucleophilic substitution , 1990 .

[19]  D. Yarkony,et al.  On the characterization of regions of avoided surface crossings using an analytic gradient based method , 1990 .

[20]  P. Hiberty,et al.  Why is SiH5- a stable intermediate while CH5- is a transition state? A quantitative curve crossing valence bond study , 1990 .

[21]  R. Rogers,et al.  Quantitation of proximity effects on rate. A case study involving dyotropic hydrogen migration within syn-sesquinorbornene disulfones carrying central substituents having different spatial demands , 1990 .

[22]  P. Hiberty,et al.  Quantitative valence bond computation of a curve crossing diagram for a model SN2 reaction: H- + CH3H' .fwdarw. HCH3 + H'- , 1989 .

[23]  F. Menger,et al.  "Transition-state modeling" does not always model transition states , 1989 .

[24]  H. Lischka,et al.  An analytical six‐dimensional potential energy surface for (HF)2 from abinitio calculations , 1988 .

[25]  K. Morokuma,et al.  Chair and boat transition states for the Cope rearrangement. A CASSCF study , 1988 .

[26]  Kendall N. Houk,et al.  Transition structures of pericyclic reactions. Electron correlation and basis set effects on the transition structure and activation energy of the electrocyclization of cyclobutene to butadiene , 1988 .

[27]  Martin J. Field,et al.  MC−SCF study of the Diels-Alder reaction between ethylene and butadiene , 1988 .

[28]  L. Raff,et al.  Computational studies of SiH2+SiH2 recombination reaction dynamics on a global potential surface fitted to abinitio and experimental data , 1988 .

[29]  S. Shaik,et al.  A theoretical treatment of nucleophilic reactivity in additions to carbonyl compounds. Role of the vertical ionization energy , 1988 .

[30]  R. Fletcher.  Practical Methods of Optimization , 1988 .

[31]  B. Trost,et al.  Origin of enhanced axial attack by sterically undemanding nucleophiles on cyclohexenones , 1987 .

[32]  K. Houk,et al.  The origin of proximity effects on reactivity: a modified MM2 model for the rates of acid-catalyzed lactonizations of hydroxy acids , 1987 .

[33]  L. Raff.  A semiempirical potential-energy surface for the 1,2-difluoroethane system , 1987 .

[34]  K. Houk,et al.  Correlated transition structure for the 1,5-sigmatropic hydrogen shift , 1987 .

[35]  K. Houk,et al.  Transition structures for intramolecular hydrogen-atom transfers: the energetic advantage of seven-membered over six-membered transition structures , 1987 .

[36]  W. Hase,et al.  A potential energy function for the hydroperoxyl radical , 1987 .

[37]  D. M. Hirst,et al.  Thermal Rate Constants for H + CH3 CH4 Recombination. II. Comparison of Experiment and Canonical Variational Transition State Theory , 1987 .

[38]  S. Shaik,et al.  Nucleophilic vinylic substitution. A theoretical study , 2002 .

[39]  W. Hase,et al.  Effect of bond stretch excitation on the attenuation of bending forces , 1986 .

[40]  William L. Hase,et al.  The sensitivity of IVR in benzene to bend–stretch potential energy coupling , 1986 .

[41]  J. Baker.  An algorithm for the location of transition states , 1986 .

[42]  J. Troe.  Relation between potential and rate parameters for reactions on attractive potential energy surfaces. Application to the reaction HO + O .dblharw. HO2* .fwdarw. H + O2 , 1986 .

[43]  K. Houk,et al.  Steric Models for Stereoselectivity of Nitrile Oxide Cycloadditions to Chiral Alkenes , 1986 .

[44]  I. Watt,et al.  Cation arxl concentration dependence of anionic rearrangements involving hydride shifts , 1986 .

[45]  William P. Jencks,et al.  A primer for the Bema Hapothle. An empirical approach to the characterization of changing transition-state structures , 1985 .

[46]  Keiji Morokuma,et al.  Determination of the lowest energy point on the crossing seam between two potential surfaces using the energy gradient , 1985 .

[47]  S. Shaik,et al.  Relationships between geometries and energies of identity SN2 transition states: the dominant role of the distortion energy and its origin , 1985 .

[48]  Ajit Banerjee,et al.  Search for stationary points on surfaces , 1985 .

[49]  A. Pross.  A General Approach to Organic Reactivity: The Configuration Mixing Model , 1985 .

[50]  Noam Agmon.  Perpendicular effects on transition-state structure: model and application to cycloadditions and sigmatropic shifts , 1984 .

[51]  H. Schlegel,et al.  Analytic Function for the H + CH3 CH4 Potential Energy Surface , 1984 .

[52]  S. Shaik.  The .alpha.- and .beta.-carbon substituent effect on SN2 reactivity. A valence-bond approach , 1983 .

[53]  J. Murdoch.  Barrier heights and the position of stationary points along the reaction coordinate , 1983 .

[54]  S. Shaik,et al.  SN2 reactivity of CH3X derivatives. A valence bond approach , 1982 .

[55]  Sason Shaik,et al.  A qualitative valence-bond approach to organic reactivity , 1982 .

[56]  Sason Shaik,et al.  What happens to molecules as they react? A valence bond approach to reactivity , 1981 .

[57]  D. DeTar,et al.  Quantitative evaluation of steric effects in SN2 ring closure reactions , 1980 .

[58]  R. B. Phillips,et al.  Diastereomeric transition states. Relative energies of the chair and boat reaction pathways in the Cope rearrangement , 1980 .

[59]  John E. Adams,et al.  Reaction path Hamiltonian for polyatomic molecules , 1980 .

[60]  A. J. Kirby,et al.  Effective Molarities for Intramolecular Reactions , 1980 .

[61]  D. DeTar,et al.  Steric effects in SN2 reactions , 1978 .

[62]  A. R. Miller.  A theoretical relation for the position of the energy barrier between initial and final states of chemical reactions , 1978 .

[63]  R. Schowen,et al.  Transition States of Biochemical Processes , 1978, Springer US.

[64]  R. Levine,et al.  Energy, entropy and the reaction coordinate: thermodynamic-like relations in chemical kinetics☆ , 1977 .

[65]  Ian Fleming,et al.  Frontier Orbitals and Organic Chemical Reactions , 1977 .

[66]  QUANTITATIVE PREDICTIONS OF STERIC ACCELERATION , 1974 .

[67]  R. Hershfield,et al.  Lactonization of coumarinic acids. Kinetic evidence for three species of the tetrahedral intermediate , 1973 .

[68]  R. Moriarty,et al.  A criticism of the use of certain bridged bicyclic hydroxycarboxylic acids as model compounds for the concept of orbital steering. , 1973, Journal of the American Chemical Society.

[69]  S. Milstien,et al.  Stereopopulation control. I. Rate enhancement in the lactonizations of 0-hydroxyhydrocinnamic acids. , 1972, Journal of the American Chemical Society.

[70]  M. J. Goldstein,et al.  Boat and chair transition states of 1,5-hexadiene , 1972 .

[71]  D. Koshland,et al.  Effect of small changes in orientation on reaction rate , 1972 .

[72]  D. Koshland,et al.  Indication of the magnitude of orientation factors in esterification , 1972 .

[73]  R. Taft,et al.  The General Applicability of a Fixed Scale of Inductive Effects. II. Inductive Effects of Dipolar Substituents in the Reactivities of m- and p-Substituted Derivatives of Benzene1,2 , 1958 .

[74]  Rudolph A. Marcus,et al.  On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I , 1956 .

[75]  George S. Hammond,et al.  A Correlation of Reaction Rates , 1955 .

[76]  Robert W. Taft,et al.  The General Nature of the Proportionality of Polar Effects of Substituent Groups in Organic Chemistry , 1953 .

[77]  J E Leffler,et al.  Parameters for the Description of Transition States. , 1953, Science.

[78]  Robert W. Taft,et al.  Linear Free Energy Relationships from Rates of Esterification and Hydrolysis of Aliphatic and Ortho-substituted Benzoate Esters , 1952 .

[79]  M. G. Evans.  Thermodynamical treatment of transition state , 1938 .

[80]  M. G. Evans,et al.  Inertia and driving force of chemical reactions , 1938 .

[81]  M. Polanyi,et al.  On the introduction of thermodynamic variables into reaction kinetics , 1937 .

[82]  M. Polanyi,et al.  Further considerations on the thermodynamics of chemical equilibria and reaction rates , 1936 .

[83]  M. G. Evans,et al.  Some applications of the transition state method to the calculation of reaction velocities, especially in solution , 1935 .