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Index *k* saddles and dividing surfaces in phase space with applications to isomerization dynamics

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10.1063/1.3602465

### Abstract

In this paper, we continue our studies of the phase space geometry and dynamics associated with index *k* saddles (*k* > 1) of the potential energy surface. Using Poincaré-Birkhoff normal form (NF) theory, we give an explicit formula for a “dividing surface” in phase space, i.e., a codimension one surface (within the energy shell) through which all trajectories that “cross” the region of the index *k* saddle must pass. With a generic non-resonance assumption, the normal form provides *k* (approximate) integrals that describe the saddle dynamics in a neighborhood of the index *k* saddle. These integrals provide a symbolic description of all trajectories that pass through a neighborhood of the saddle. We give a parametrization of the dividing surface which is used as the basis for a numerical method to sample the dividing surface. Our techniques are applied to isomerizationdynamics on a potential energy surface having four minima; two symmetry related pairs of minima are connected by low energy index 1 saddles, with the pairs themselves connected via higher energy index 1 saddles and an index 2 saddle at the origin. We compute and sample the dividing surface and show that our approach enables us to distinguish between concerted crossing (“hilltop crossing”) isomerizing trajectories and those trajectories that are not concerted crossing (potentially sequentially isomerizing trajectories). We then consider the effect of additional “bath modes” on the dynamics, by a study of a four degree-of-freedom system. For this system we show that the normal form and dividing surface can be realized and sampled and that, using the approximate integrals of motion and our symbolic description of trajectories, we are able to choose initial conditions corresponding to concerted crossing isomerizing trajectories and (potentially) sequentially isomerizing trajectories.

© 2011 American Institute of Physics

Received 06 April 2011
Accepted 03 June 2011
Published online 23 June 2011

Acknowledgments: P.C. and S.W. acknowledge the support of the Office of Naval Research Grant No. N00014-01-1-0769. P.C., G.S.E., and S.W. would like to acknowledge the stimulating environment of the NSF sponsored Institute for Mathematics and its Applications (IMA) at the University of Minnesota, where this work was begun.

Article outline:

I. INTRODUCTION

II. THE POINCARÉ-BIRKHOFF NORMAL FORM IN A PHASE SPACE NEIGHBORHOOD OF AN INDEX *k* SADDLE

A. A normally hyperbolic invariant manifold

B. Accuracy of the normal form

III. CROSSING AND CONCERTED CROSSING TRAJECTORIES

IV. THE DIVIDING SURFACE ASSOCIATED WITH INDEX *k* SADDLES

A. Definition of dividing surface in the general case

B. Index 1 saddles

C. Explicit parametrization of the DS for quadratic Hamiltonians

D. Sampling the dividing surface

V. INDEX-2 SADDLES: MODEL POTENTIALS

A. 2 DoF 4-well model potential

B. Sampling trajectories on the DS

C. Trajectory studies of isomerizationdynamics

D. Saddle crossing in the presence of bath modes

1. System-bath Hamiltonian

2. Sampling trajectories on the extended DS for 4 DoF

VI. SUMMARY AND CONCLUSIONS

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2011-06-23

2014-04-19

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