论文信息 - ON FINDING TRANSITION STATES

ON FINDING TRANSITION STATES

An algorithm for locating transition states on a potential energy surface is described. The most important feature of the algorithm, which makes explicit use of the second derivative matrix of the potential surface, is that it is able to ’’walk uphill’’ from the minimum on a potential surface to the transition state essentially automatically. The method is illustrated by application to a two dimensional model problem, to the vinylidene–acetylene rearrangement (H2C = C:↔HC≡CH), and to the dissociation and rearrangement of formaldehyde (H2CO↔H2+CO, HCOH). The algorithm is also seen to provide an improved way of following a reaction path from a transition state down to reactants or products.

W. Miller | C. Cerjan

[1] J. Pople,et al. Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals , 1969 .

[2] James W. McIver,et al. Structure of transition states in organic reactions. General theory and an application to the cyclobutene-butadiene isomerization using a semiempirical molecular orbital method , 1972 .

[3] J. Brickmann,et al. Quantum states of intramolecular nuclear motion with large amplitudes: Pseudorotation of trigonal bipyramidal molecules , 1975 .

[4] D. Poppinger,et al. On the calculation of transition states , 1975 .

[5] Kazuhiro Ishida,et al. The intrinsic reaction coordinate. An ab initio calculation for HNC→HCN and H−+CH4→CH4+H− , 1977 .

[6] Henry F. Schaefer,et al. The photodissociation of formaldehyde: Potential energy surface features , 1979 .

[7] K. Müller,et al. Location of saddle points and minimum energy paths by a constrained simplex optimization procedure , 1979 .