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Introduction.—Transition state theory (TST) was The problem solved in this Letter is the construction of
developed in the 1930s [1] as a way to determine absolute hypersurfaces of no return in the phase-space of strongly
chemical reaction rates. An essentially thermodynamic coupled, multidimensional systems. Our solution leads
picture emerged from the original research of Eyring [2] naturally to the multidimensional generalization of a saddle
and this continued to be the dominant formulation of the “point” and its associated separatrices.
theory for many decades. In parallel with Eyring’s work, a Until very recently, neither theoretical understanding
dynamical picture was also being developed by Wigner [3] nor computing power was adequate to explore phase-space
and this turns out to have considerable advantages. Not the transport beyond the well-known two degrees-of-freedom
least of these is that Wigner’s formulation quickly leads (“2dof”) limit [10]. However, with recent advances in dy-
to the recognition that the transition state (TS) is actually namical systems theory [11], especially concerning nor-
a general property of all dynamical systems, provided that mally hyperbolic invariant manifolds (NHIM) [12], the
they evolve from “reactants” to “products.” The TS, there- classical theory of chemical reactions can now be an-
fore, is not confined to chemical reaction dynamics [4], but chored rigorously in nonlinear dynamics. Indeed, this
it also controls rates in a multitude of interesting systems, Letter makes explicit the long-sought classical structures
including, e.g., the rearrangements of clusters [5], the that act as transition states in phase-space beyond 2dof.
ionization of atoms [6], conductance due to ballistic As we will show, the rigorous way to describe the notion
electron transport through microjunctions [7], and diffu- of a “barrier” in phase-space is through invariant mani-
sion jumps in solids [8]. Since transition state theory is folds. “Invariance” signifies that trajectories starting on
fundamental for transformations in n degree-of-freedom the manifold must remain on the manifold for the future
systems, the work summarized here represents a general and throughout the past. Hence, no trajectory can cross an
formulation of the nonlinear dynamics and geometry of invariant manifold. These manifolds, as indeed all other
classical reaction dynamics. It hinges on finding, for multidimensional structures in this Letter, become famil-
the first time, the dynamically exact higher-dimensional iar objects when viewed in 2dof: For example, NHIM’s
structures (separatrices, dividing surfaces) which regulate reduce to none other than periodic orbits. Our treatment
transport between qualitatively different states (reagents is general, and because it relies on recent advances in dy-
and products) in three or more degrees of freedom. namical systems theory, we provide a “user’s guide” which
Stated succinctly, TST postulates the existence of a we then apply to a realistic system. The following review
minimal set of states that all reactive trajectories must of 2dof systems will set the terms for extension to more
cross and which are never encountered by nonreactive degrees of freedom.
trajectories. While the original idea of a TS was expressed Lower-dimensional theory.— Current understanding of
as a dividing surface in coordinate space, Wigner rec- the transition state as a geometrical structure in 2dof sys-
ognized [9] that a rigorous treatment must seek dividing tems has been greatly aided by the discovery [13] that
surfaces in phase space which separate reactants from projection of an unstable periodic orbit into configura-
products and which no trajectory passes through more tion space defines a surface separating reactants and prod-
than once. Enforcing this “no recrossing” requirement ucts and is therefore a “periodic orbit dividing surface” or
has been a major obstacle to applying TST in strongly PODS. In phase-space, the stable and unstable manifolds
coupled, multidimensional systems. Consequently, TST of this orbit partition the energy shell. This partitioning
has remained a configuration-space theory that has further is invariant and separates the reactive and nonreactive dy-
been confined to low dimensions for which the dividing namics. It is not generally recognized that the defining
surfaces can be found in practice. periodic orbit also bounds a surface in the energy shell.
This surface partitions the energy shell into reactant and simple rotation in phase-space. In the language of reac-
product regions and is not invariant. Defined in this way tion dynamics, the coordinates 共j, pj 兲 are known as the
the surface is a surface of no return [6] and thus consti- reaction coordinates, whereas the remaining coordinates
tutes the phase-space transition state. It also provides an describe the “bath.” In the j-pj phase portrait, when the
unambiguous measure of the flux between reactants and saddle is at the origin, trajectories are said to be reacting
products [14–16]. These facts will be useful when we if j changes sign. We will show how to generalize this
present the multidimensional versions of these structures. simple case to a fully nonlinear setting.
Beyond 2dof, periodic orbits, and their stable and un- Returning to (1), the corresponding Hamiltonian vector
stable manifolds [11], do not have the right dimensionality field is given by
to partition the energy shell. Nevertheless, early insights
[17] and recent numerical evidence from molecular ≠H ≠f1 ≠f2
dynamics calculations [5] suggest the existence of higher- qᠨ i 苷 苷 vi pi 1 1 ,
≠pi ≠pi ≠pi
dimensional structures with many of the regulatory
features of the PODS, and it is precisely these phase-space ≠H
pᠨ i 苷 2
structures which will be exhibited in this Letter. ≠qi
Phase-space structure and the transition state for n- ≠f1 ≠f2
degree-of-freedom nonlinear Hamiltonians.— Consider an 苷 2vi qi 2 2 , i 苷 1, . . . , n 2 1 , (3)
≠qi ≠qi
arbitrary Hamiltonian vector field, and suppose it has an
equilibrium point at which the matrix associated with the ≠H ≠f1
linearization of the Hamiltonian vector field about the equi- qᠨ n 苷 苷 lqn 1 qn ,
≠pn ≠I
librium point has eigenvalues 6ivj , j 苷 1, . . . , n 2 1,
and 6l. Moreover, assume that the submatrix correspond- ≠H ≠f1
pᠨ n 苷 2 苷 2lpn 2 pn ,
ing to the imaginary eigenvalues is semisimple (i.e., the ≠qn ≠I
complexification is diagonalizable). Using Hamiltonian
normal form theory [18], one can construct a sequence where the last two equations denote the motion in the
of local, nonlinear transformations of the coordinates that reaction coordinates. The rest refer to dynamics in the
transform the Hamiltonian into bath modes.
A multidimensional saddle “point”.—The dynamics
X
n21 occurs in the 2n-1-dimensional energy surface given
vi 2
H 苷 共pi 1 qi2 兲 1 lqn pn by setting H in (1) to be a positive constant h. If we
i苷1 2 set qn 苷 pn 苷 0 in (3), then qᠨ n 苷 pᠨ n 苷 0. Therefore
1 f1 共q1 , . . . , qn21 , p1 , . . . , pn21 , I 兲 qn 苷 pn 苷 0 is a 2n-2 dimensional invariant manifold.
1 f2 共q1 , . . . , qn21 , p1 , . . . , pn21 兲 , (1) Its intersection with the 2n-1-dimensional energy surface,
denoted Mh2n23 , is given by
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VOLUME 86, NUMBER 24 PHYSICAL REVIEW LETTERS 11 JUNE 2001
manifold (4) is invariant regardless of the size of the non- decouple from the oscillatory dynamics at the linear level)
linearity. Moreover, it is also of saddle type with respect and has 2n-2 dimensional stable and unstable manifolds
to stability in the transverse directions [19]. in the 2n-1 dimensional energy surface [20]. Recent dis-
However, a key feature of NHIM’s is that they persist coveries concerning regularity in complex reaction paths
under perturbation. Therefore, if we first need to obtain [5], anticipated by Miller [17] and executed by Hernandez
the form of (1) by applying normal form theory, then we and Miller [21], suggest that the decoupling of the reac-
are restricted to a sufficiently small neighborhood of the tion degree-of-freedom from the bath, and the reduction of
equilibrium point. In this case the nonlinear terms are complex reactive Hamiltonians to (1), is general.
much smaller than the linear terms. Therefore, (4) is a Multidimensional separatrices.— Another advantage of
deformed saddle sphere (since the saddle-point dynamics computing the normal form is that the unstable and stable
manifolds of Mh2n23 are known explicitly:
( É
X
n21
vi
W u
共Mh2n23 兲 苷 共q1 , . . . , qn , p1 , . . . , pn 兲 共 pi2 1 qi2 兲 1 f2 共q1 , . . . , qn21 , p1 , . . . , pn21 兲
i苷1 2
)
苷 h 苷 const . 0, pn 苷 0 , (5)
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VOLUME 86, NUMBER 24 PHYSICAL REVIEW LETTERS 11 JUNE 2001
5481