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International Journal of Bifurcation and Chaos, Vol. 18, No.

4 (2008) 11271149 c World Scientic Publishing Company

CLASSICAL MECHANICS OF DIPOLAR ASYMMETRIC TOP MOLECULES IN COLLINEAR STATIC ELECTRIC AND NONRESONANT LINEARLY POLARIZED LASER FIELDS: ENERGY-MOMENTUM DIAGRAMS, BIFURCATIONS AND ACCESSIBLE CONFIGURATION SPACE
CARLOS A. ARANGO and GREGORY S. EZRA Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, NY 14853, USA gse1@cornell.edu Received November 21, 2006; Revised May 23, 2007
We study classical energy-momentum (E-m) diagrams for rotational motion of dipolar asymmetric top molecules in strong external elds. Static electric elds, nonresonant linearly polarized laser elds, and collinear combinations of the two are investigated. We treat specically the molecules iodobenzene (a nearly prolate asymmetric top), pyridazine (nearly oblate asymmetric top), and iodopentauorobenzene (intermediate case). The location of relative equilibria in the E-m plane and associated bifurcations are determined by straightforward calculation, with analytical results given where possible. In cases where analytical solutions cannot be obtained, we resort to numerical solutions, while keeping a geometrical picture of the nature of the solutions to the fore. The classication we obtain of the topology of classically allowed rotor conguration space regions in the E-m diagram is of potential use in characterization of energy eigenstates of the corresponding quantum mechanical problem. Keywords: Classical mechanics; molecular rotation; relative equilibria; bifurcations.

1. Introduction
The study of rigid body motion is one of the most important topics in classical and quantum mechanics [Klein & Sommerfeld, 1965; Casimir, 1931; Deprit, 1967; Arnold, 1978; Zare, 1988; Arnold et al., 1988; Deprit & Elipe, 1993; Goldstein et al., 2002]. Of particular importance are the integrable cases of the rigid body problem [Oshemkov, 1991; Bolsinov & Fomenko, 2004], which include the free asymmetric top (Euler top) [Klein & Sommerfeld,

1965; Arnold, 1978; Arnold et al., 1988], the symmetric top in a uniform external gravitational eld (Lagrange top) [Arnold et al., 1988; Cushman & Bates, 1997], and the Kovalevskaya top [Arnold et al., 1988; Perelemov, 2002]. The theory of rigid body motion also provides the basis for analysis and interpretation of the rotational dynamics and spectra of semi-rigid molecules [Casimir, 1931; Zare, 1988; Townes & Schawlow, 1975; Harter, 1988; Kroto, 1992; Bunker & Jensen, 1998]. In molecular

Current address: Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada 1127

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C. A. Arango & G. S. Ezra

terms the Euler top is simply a free asymmetric top molecule [Zare, 1988; Harter, 1988; Kroto, 1992], the Lagrange top models a symmetric top molecule with a dipole moment in an electric eld [Kroto, 1992; Kozin & Roberts, 2003], while there does not appear to be an obvious molecular analogue for the Kovalevskaya top. Breaking the symmetry of the moment of inertia tensor in the Lagrange top results in the nonintegrable problem of an asymmetric top in a static eld. Molecular examples of these two cases are iodobenzene (near prolate) [Peronne et al., 2003, 2004] and pyridazine (near oblate) [Li et al., 1998] in a static electric eld. The rotational constants of the molecule iodopentauorobenzene make it a more generic example of an asymmetric rotor [Poulsen et al., 2004]. The general problem of classical-quantum correspondence [Gutzwiller, 1990; Child, 1991] is of great interest for both integrable and nonintegrable rotor systems. Various aspects of the classicalquantum correspondence have been studied for diatomic molecules in tilted elds, i.e. noncollinear static electric and nonresonant linearly polarized laser elds [Arango et al., 2005]. The integrable collinear case exhibits the phenomenon of monodromy [Cushman & Bates, 1997] both classically and quantum mechanically [Arango et al., 2004]. For the nonintegrable case of tilted elds the rotor motion tends to be integrable in both low-energy (pendular) and high-energy (free-rotor) limits, and chaotic at intermediate energies, with the degree of chaos controllable by variation of the angle between the elds [Arango et al., 2005]. For collinear elds the system is integrable, with both the energy E and the projection of the angular momentum into the space xed z-axis, m, as constants of motion. The eective potential Ve (; m) for a given value of m exhibits extrema in the (polar) coordinate, which dene the relative equilibria [Arnold, 1978; Arnold et al., 1988; Smale, 1970]. Plotting the location of these extrema in the E-m plane gives the energy-momentum diagram for the system [Arango, 2005]. The E-m diagram provides a useful global classication of the rotor dynamics, as distinct regions of the E-m plane are associated with different allowed types of motion of the diatomic. For symmetric tops in electric elds similar diagrams can be constructed [Kozin & Roberts, 2003], and analysis of classical symmetric top E-m and E-k diagrams helps understand the organization of the quantum level spectrum [Kozin & Roberts, 2003].

The problem of a dipolar asymmetric top in a static external eld is nonintegrable [Arango, 2005; Grozdanov & McCarroll, 1996], as is the problem of a polarizable asymmetric top in a nonresonant laser eld [Arango, 2005]. For asymmetric tops in either static or laser elds or collinear superpositions of the two, the angular momentum projection m is a constant of motion. Although the complicated form of the kinetic energy does not allow us to separate an eective potential as straightforwardly as in the diatomic or the symmetric top case, it is still possible to dene an eective or amended potential [Arnold et al., 1988; Bolsinov & Fomenko, 2004; Smale, 1970] for the class of motions in which the asymmetric top molecule rotates with constant Euler angles and (the third Euler angle is an ignorable coordinate). The energies of the extrema of this potential for given values of m again dene an energy-momentum diagram [Arnold, 1978; Smale, 1970; Iacob, 1971; Katok, 1972; Tatarinov, 1974; Artigue et al., 1986], which can be used to classify the motions of the asymmetric top. The asymmetric top in an external static electric eld is an example of a dynamical system with symmetry [Smale, 1970; Arnold et al., 1988; Marsden, 1992; Marsden & Ratiu, 1999]. The potential energy and Hamiltonian in this case are invariant with respect to rotations about the space-xed eld direction. There is therefore an associated constant of the motion m, the projection of the angular momentum vector j onto the external eld axis, in addition to the energy E. The mapping of the system phase space onto the E-m plane is called the energy-momentum map [Arnold et al., 1988; Smale, 1970; Marsden, 1992; Marsden & Ratiu, 1999]. Critical points of this mapping dene the bifurcations sets in the E-m plane, which form the boundaries of regions of qualitatively dierent types of classical motion [Bolsinov & Fomenko, 2004; Smale, 1970]. Following the fundamental work of Smale [1970], applications of these concepts were made to integrable rotor problems [Iacob, 1971], asymmetric rotors in an external gravitational eld [Katok, 1972], and symmetric [Tatarinov, 1973] and asymmetric [Tatarinov, 1974] rotors in more complicated potentials. Relative equilibria have also been studied for rotating semi-rigid molecules in the absence of external elds [Montaldi & Roberts, 1999; Kozin et al., 2000] and for transition states in rotationally inelastic collisions [Wiesenfeld et al., 2003].

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In the present paper we study E-m diagrams of relative equilibria for molecular asymmetric tops for several molecule-eld congurations of physical interest [Stapelfeldt & Seideman, 2003; Seideman & Hamilton, 2005]: a static electric eld; a nonresonant linearly polarized laser eld; both elds in a collinear combination. For the eld strengths considered, the free asymmetric top motion is strongly perturbed. The associated E-m diagrams are obtained for the most part analytically. Our aim here is to understand the nature of the rotor motions associated with dierent regions and curves in the E-m diagrams for physically relevant values of the eld parameters. We also study the topological classication of the allowed - conguration space of the system in terms of their (multivalued) genus [Arnold et al., 1988]. An extension of these results, to be discussed in a future paper, involves comparison of computed quantum mechanical eigenstate probability densities with the boundaries of classically allowed regions in - conguration space. The comparisons indicate that the classical mechanical methods developed here provide a promising foundation for the dicult task of classifying the quantum levels of the complex system consisting of an asymmetric rotor in external elds [Block et al., 1992; Moore et al., 1999; Kanya & Oshima, 2004]. We mention that the approach adopted here may be thought of as the analogue for perturbed rotor systems of the methods applied by Kellman and coworkers [Kellman, 1995; Rose & Kellman, 2000] to vibrational problems exhibiting a single conserved vibrational (superpolyad) quantum number (see also [Cooper & Child, 2005]). There have been many studies of the classical dynamics of a rigid asymmetric top rotating about a xed point in a gravitational eld (this is the classic heavy top problem); see, for example [Klein & Sommerfeld, 1965; Arnold et al., 1988; Iacob, 1971; Katok, 1972; Galgani et al., 1981; Artigue et al., 1986; Chavoya-Aceves & Pina, 1989; Lewis et al., 1992; Broucke, 1993; Gashenenko & Richter, 2004]. Katok [1972] and Gashenenko and Richter [2004] obtained E-m diagrams and analyzed bifurcations of relative equilibria in the E-m plane. These authors also classied the topology of accessible system conguration space. We present here a similar analysis for several molecular examples of an asymmetric top molecule possessing a dipole moment in a static electric eld. In the

spirit of Katoks analysis [Katok, 1972], we use straightforward analytical and geometric methods to build the E-m diagram for the molecules of interest. Katoks treatment was generalized by Tatarinov [1974] (see also [Arnold et al., 1988]) to include more complicated gravitational perturbations of the rotational dynamics of an asymmetric top. Although given for a specic potential, Tatarinovs analysis can be mapped directly onto the molecular case of an asymmetric top in collinear elds [Arango, 2005]. Following Tatarinov, we obtain E-m diagrams for asymmetric molecules of physical interest, and study bifurcations and other characteristic features of the problem, including the topology of the - conguration space and its classication according to the genera of the (connected) allowed regions [Arnold et al., 1988]. This paper is organized as follows. First in Sec. 2 we derive the Hamiltonian for asymmetric tops in the general tilted elds case, with the aim of introducing our notation and conventions. In Sec. 3 we treat the molecules in a static electric eld, while in Sec. 4 we study the same molecules in a nonresonant linearly polarized laser eld. In Sec. 5 we analyze these molecules in collinear elds. Section 6 provides the conclusion. Finally we mention that, the advantages of alternative approaches notwithstanding [Cushman, 2005], all calculations reported here have been carried out using polar coordinates.

2. Hamiltonian for the Asymmetric Top in Combined Fields 2.1. General case: Tilted elds
We use the y-convention [Zare, 1988] to dene the three Euler angles (, , ) describing the orientation of the body-xed frame with respect to labxed frame. In the body-xed frame the kinetic energy of the free asymmetric top can be written in terms of the components of the angular momentum j = (j1 , j2 , j3 ) and the three components of the (diagonal) moment of inertia tensor I = diag(I1 , I2 , I3 ) T =
2 j2 j2 j1 + 2 + 3 . 2I1 2I2 2I3

(1)

For an asymmetric top, I1 = I2 = I3 . In terms of the Euler angles and their conjugate momenta

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C. A. Arango & G. S. Ezra

(p , p , p ) the body-xed components of j are j1 = p sin p j2 = p cos + p j3 = p so that


2 2 2 j 2 = j1 + j2 + j3

cos + p cos cot , (2a) sin sin p sin cot , (2b) sin (2c)

The Hamiltonian of the asymmetric top in tilted elds can be written from Eqs. (4), (7) and (6) as H = T + VS + VL . (8)

= p2 +

1 (p p cos )2 + p2 . sin2

(3)

Note that the potential VS + VL is a function of the angle , so that m is not conserved. The asymmetric top in tilted elds is therefore a physically signicant rotor problem with three degrees of freedom. For collinear elds, = 0, the angle is not present in H and p = m is then a constant of the motion. In the remainder of this paper we consider the collinear case only.

From (1), the kinetic energy T = T (, , , p , p , p ) is then T = cos 1 (p cos p ) p sin + 2I1 sin
2

2.2. Collinear elds


The Hamiltonian for an asymmetric top molecule in collinear elds can be rewritten as 1 H = (I1 j) j + V (, ), 2 with V (, ) = cos 2 sin2 sin2 3 cos2 . (9)

2 p2 1 sin (p p cos ) + + . p cos + 2I2 sin 2I3 (4)

Immediately we see that is an ignorable coordinate and p = m, the projection of j into the space xed z-axis, is a constant of the motion for the free top. If the polarizability in the molecule-xed frame is given by the diagonal tensor = diag(1 , 2 , 3 ), the interaction with a nonresonant laser eld polarized along the space-xed z-axis is [Stapelfeldt & Seideman, 2003] VL = 2 L [1 + (2 1 ) sin2 sin2 4 (5)

(10)

In terms of the Euler angles and their time derivatives the body-xed components of the angular momentum are j1 = I1 ( sin sin cos ), j2 = I2 ( cos + sin sin ), j3 = I3 ( cos + ). (11a) (11b) (11c)

+ (3 1 ) cos2 ],

The projection of j onto the space-xed unit vector ez = (0, 0, 1) is given in terms of the direction cosine matrix C as m = C3 j, where C3 = (C31 , C32 , C33 ) = (sin cos , sin sin , cos ), is the vector of body-xed components of ez . (12)

with 2 is proportional to the intensity of the laser L eld. Omitting the angle-independent term (which produces a constant shift in energy) we obtain VL = 2 sin2 sin2 3 cos2 , (6) with 2 = (2 1 )2 /4 and 3 = (3 L 1 )2 /4. Assuming the dipole moment to lie along L the molecule-xed z -axis, the interaction with a static electric eld tilted through an angle with respect to the space-xed z-axis and lying in the space-xed xz-plane is VS = d0 S (cos cos + sin cos sin ), (7)

(13)

2.3. Determination of relative equilibria


As the angle is ignorable, we consider relative equilibria dened by the conditions = 0, and = 0 [Katok, 1972]. These relative equilibria in general dene periodic orbits in the full rotor phase space.

where d0 is the magnitude of the electric dipole moment and S is the strength of the static eld.

Classical Mechanics of Dipolar Asymmetric Top Molecules

1131

Using these conditions in Eqs. (11), and rewriting in terms of C3 we obtain (14) j = (IC3 ). The equation for m, (12), can be rewritten as m = (IC3 ) C3 , (15) which can be used to express in terms of m and 3 . Substituting the resulting expression for j, C j= m(IC3 ) , (IC3 ) C3 (16)

solution curves. Zeroes of the relevant functions are found by interpolation along the curve, yielding values of and that solve (18) for given m. Finally, the eective potential (17) is evaluated at each of these solution points, which in general have dierent energies for a given m. The calculation is repeated for dierent values of m to obtain the complete E-m diagram. To clarify the general procedure just outlined, consider the Euler problem (free asymmetric top), with = 2 = 3 = 0. Equations (18) in this case are sin cos (I1 cos2 + I2 sin2 I3 )m2 Vm = [(IC3 ) C3 ]2 = 0, (21a) sin cos sin2 (I2 I1 )m2 Vm = = 0. (21b) [(IC3 ) C3 ]2 The common denominator is never zero, and is sufcient to nd the zeros in the numerators. The solutions = 0, satisfy both equations simultaneously giving the solution set A = {0, } [0, 2). In the cartesian product the rst set gives the possible values of the coordinate, the second set the possible values of the coordinate. Setting = 0, /2, , or 3/2 solves Eq. (21b); substituting these values into (21a) gives sin cos (I3 I1 )m2 = 0, = 0, , = 3 , . 2 2 (22a) (22b)

into the Hamiltonian (9) gives the eective or amended potential [Arnold et al., 1988; Bolsinov & Fomenko, 2004; Katok, 1972; Tatarinov, 1974] for an asymmetric top molecule in collinear elds Vm (, ) = m2 + V (, ). 2(IC3 ) C3 (17)

Relative equilibria with = 0, = 0 are found from the eective potential (17) solving the equations Vm m2 (IC3 ) C3 V = + = 0, [(IC3 ) C3 ]2 m2 (IC3 ) C3 V Vm = + = 0, [(IC3 ) C3 ]2 with C3 C3 and V = sin 22 sin cos sin2 + 23 sin cos , V = 22 sin cos sin2 . (20a) (20b) (18a) (18b)

= (cos cos , sin cos , sin ), = (sin sin , cos sin , 0)

(19a) (19b)

sin cos (I3 I2 )m2 = 0,

For these equations = 0, /2, , are solutions. In the same notation used before the new solutions are B = {/2} {0, }, and C = {/2} {/2, 3/2}. The complete solution set for the Euler problem is SE = A B C. For each of these sets is possible to obtain a Vm -m curve simply by evaluating the eective potential on each of the solution sets Vm (A) = Vm (B) = Vm (C) = m2 , 2I3 m2 , 2I1 m2 . 2I2 (23a) (23b) (23c)

In general the solutions of Eq. (18) depend on m. For a given m the zero set of Vm / (respectively, Vm /) in the - space gives the solution set for Eq. (18a) (respectively, (18b)). The solution set typically consists of (possibly disjoint) curves in the - plane. In practice (see below), we are able to give a natural parametrization of each of these solution curves, so that the general solution of Eqs. (18) is obtained by evaluating Vm / (respectively, Vm /) along each of the particular

The E-m diagram consists of three parabolas and the regions enclosed between them. This diagram is shown in Fig. 1 for the three molecules considered here (cf. Sec. 3.4 of Arnold [1988]; Ch. 14 of

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C. A. Arango & G. S. Ezra


10 8 6 10 8 6 E 4 2 0 4 2 0

(a)

(b)

10 8 6 E 4 2 0 4 3 2 1 0 m 1 2 3 4

(c) Fig. 1. E-m diagrams for free asymmetric top molecules (Euler tops). (a) Iodobenzene; (b) Pyridazine; (c) Iodopentauorobenzene.

Bolsinov and Fomenko [2004]). The dierent lines represent the three parabolas (23) and correspond physically to rotations of the top about the body xed axes (in a positive or negative sense). The region below the red curve is physically inaccessible. In the axis convention used to obtain the asymmetric top Hamiltonian the red curve, Eq. (23b), corresponds to stable rotation about the body xed x-axis; the green parabola, Eq. (23c), to an unstable rotation about the y-axis, and the blue curve to a stable rotation about the z-axis. For a given (E,m) point in Fig. 1, the eective potential (17) gives an equation to solve in or . The solutions are found as contours of constant Vm = E in the - conguration space, the Poisson sphere S 2 . These contours dene the classically accessible (Vm E) and forbidden (Vm > E) regions for given E and m. The topology of the different solutions on the (, ) sphere is characterized

by the (multi-valued) genus dened as in Arnold [1988]: the connected region B has genus if B is dieomorphic to the sphere S 2 with disjoint discs removed. If the classically accessible region is disconnected, then it is assigned a multivalued genus 1 , 2 , . . . , where each k is the genus of one of the components. Figure 2 shows the classically accessible regions (in black) of S 2 for iodopentauorobenzene. Panel 2(a) represents an (E, m) point located between the red and green parabolas in Fig. 1(c); the multivalued genus is 1,1 since there are two disjoint classically accessible regions and from the point of view of each there is one white disc removed from the sphere. In the same way, panel 2(b) is the accessible region for a (E, m) point located between the green and blue parabolas of 1(c), but now the genus is 2 since two white discs are removed. Finally the region above the blue parabola in 1(c) has 0

Classical Mechanics of Dipolar Asymmetric Top Molecules

1133

2 1.5

1 0.5 0 0 0.25 0.5 0.75 1 /


(a)

0.25 0.5 0.75 1 /


(b)

0.25 0.5 0.75 1 /


(c)

Fig. 2. Regions of classically allowed motion in - conguration space for iodopentauorobenzene for the dierent regions of Fig. 1(c).

genus since all the sphere is classically accessible (panel 2(c)).

3. E -m Diagram for Asymmetric Top Molecules in Static Electric Fields


Energy-momentum diagrams for the asymmetric top in an external gravitational eld have been studied by Katok [1972] and by Gashenenko and Richter [2004]. An important conclusion in these works is that, in the study of relative equilibria and their bifurcations in asymmetric tops, the relevant parameters are the ratios between two of the moments of inertia and the third one, e.g. I1 /I3 and I2 /I3 . In this section we treat as examples three asymmetric top molecules of recent theoretical and experimental interest [Kozin & Roberts, 2003; Stapelfeldt & Seideman, 2003]: the near-prolate top iodobenzene (C6 H5 I) [Poulsen et al., 2004; Bulthuis et al., 1997], the near-oblate top pyridazine (C4 H4 N2 ) [Kozin & Roberts, 2003; Li et al., 1998], and the intermediate case iodopentauorobenzene [Poulsen et al., 2004]. Relevant physical parameters for these molecules are given in Table 1.
Table 1. Molecule C6 H5 Id C4 H4 N2 e C6 F5 If
a b

In Fig. 3 we show the denition of the body xed frame for these molecules. The moment of inertia Ii is related to the rotational constant Bi by Bi = (2Ii )1 . The rotational constants Bi , the eld parameter , and the energy are all scaled by B3 . For iodobenzene an electric eld of S = 25 kVcm1 [Bulthuis et al., 1997] gives /B3 = 4.52; for pyridazine a eld of strength S = 56 kVcm1 [Li et al., 1998] gives /B3 = 19.04; in iodopentauorobenzene, an electric eld of S = 25 kVcm1 gives /B3 = 18.93 [Kozin & Roberts, 2003; Poulsen et al., 2004; Bulthuis et al., 1997]. For the asymmetric top molecule in an electric eld, the relative equilibria are found by solving the equations (setting 2 = 3 = 0 in Eqs. (18)): sin cos I1 cos2 + I2 sin2 I3 m2 Vm = [(IC3 ) C3 ]2 + sin = 0, sin cos sin2 (I2 I1 )m2 Vm = = 0, [(IC3 ) C3 ]2 (24a) (24b)

Molecular parameters. d0 b 1.70 4.14 1.54g 1 c 10.2 5.84 10.5 2 15.3 10.29 17.9 3 21.5 10.35 23.8 Point Group C2v C2v C2v

B3 a 0.189 0.208 0.034

B1 /B3 0.117 0.490 0.264

B2 /B3 0.132 0.970 0.359

Rotational constant in cm1 Dipole moment in Debye c Polarizabilities in 3 A d Iodobenzene [Poulsen et al., 2004; Bulthuis et al., 1997] e Pyridazine [Innes et al., 1988; Hinchlie & Soscn, 1994] u f Iodopentauorobenzene [Poulsen et al., 2004] g ab-initio 3-21G

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C. A. Arango & G. S. Ezra

x y

given by A1 = {0} [0, 2), and A2 = {} [0, 2). The Vm -m curves for these subsets are Vm (A1 ) = Vm (A2 ) = m2 , 2I3 m2 + . 2I3 (26a) (26b)

The solutions = 0, /2, , 3/2 to (24b) must be substituted into (24a). After rearranging and dividing by I3 , this gives (1 i1 )m2 cos = I3 [i1 + (1 i1 ) cos2 ]2 , (27a)

x z

(1 i2 )m cos = I3 [i2 + (1 i2 ) cos ] , (27b) for = 0, and = /2, 3/2 respectively, and i1 I1 /I3 , i2 I2 /I3 . For the case I1 > I2 > I3 , i.e. i1 > i2 > 1, the right-hand sides (RHS) of these equations are functions with maxima at = 0, and a minimum at = /2; the left-hand sides (LHS) are functions with a minimum at = 0, a maximum at = , and a xed zero at = /2. In Fig. 4, the LHS and RHS of these equations are plotted in order to show the nature of the solutions. As m is increased the amplitude of variation of the solid curve about zero gets larger until it intersects the dashed line at = 0, at which point a solution of the equation is obtained. Since the curves do not change their shape, there can exist only one solution for each of the Eqs. (27) for a given m. This unique intersection gives a value of , which together with the respective gives the solution of Eqs. (27). The form of the curves indicates that the intersection occurs initially at = 0 and then moves to larger values of as |m| increases, i.e. the solution A1 bifurcates twice, rst for the = 0, curve and then for the = /2, 3/2 curve. Since the solid line is always zero at = /2, the intersection of the two curves cannot go beyond this point, this means that for large values of m the asymmetric top in an electric eld behaves like an Euler top. The bifurcations in the E-m and E- diagrams are shown in Fig. 5. For iodobenzene we set /B3 = 10, for pyridazine /B3 = 20, and for iodopentauorobenzene /B3 = 20. In the E-m diagrams there are four regions delimited by dierent color curves. The allowed conguration space corresponding to the regions delimited by the red and green curves have genus 1,1; those between the green and the blue curves have genus 2; between the blue and magenta curves the

x y

Fig. 3. Denition of body-xed coordinate frames for iodobenzene (upper panel), pyridazine (middle panel), and iodopentauorobenzene (lower panel). Hydrogen and uorine atoms are represented by white circles, carbon atoms by black circles, and nitrogen and iodine atoms by grey circles, respectively. In each case the x-axis is perpendicular to the plane of the molecule, and the dipole moment points along the bodyxed z-axis.

where (IC3 ) C3 = I1 sin2 cos2 + I2 sin2 sin2 + I3 cos2 . (25) Again we have the solution set A = {0, } [0, 2). There are two solution subsets A1 A, and A2 A,

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1135

0 (1i1) m
2

0 (1i2) m
2

I3 I3 i1
2

I3 I3 i22

0.25

0.5 0.75 /

0.25

0.5 0.75 /

Fig. 4. Plots of RHS (dashed), and LHS (solid) of Eqs. (27) for m values at which curves do not intersect. Left panel: Eq. (27a); right panel: Eq. (27b).

4 3

10 E

2 1 0 1 0
(a)

10

20

0.25

0.5
(b)

0.75

10 E

4 2 0 0
(c)

20

40

0.25

0.5
(d)

0.75

10 8 6 4 2 0

10 E

10

20

0.25

0.5

0.75

m
(e)

/
(f)

Fig. 5. E-m and E- bifurcation diagrams for dipolar asymmetric top molecules in a static electric eld. (a), (b) iodobenzene (/B3 = 10); (c), (d) pyridazine (/B3 = 20); (e), (f) iodopentauorobenzene (/B3 = 20).

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C. A. Arango & G. S. Ezra

genus is 1, and above the magenta curve the genus 0. It can be seen that the only dierence between these diagrams and those for the Euler top is the presence of the region with genus 1. The curves themselves represent rotations in at constant and . Associated values for given energy are shown using the curve colors in panels 5(b), 5(d) and 5(f). The red curve is a stable rotation with = 0, and ; the green curve is unstable with = /2, 3/2 and in the RHS panels. The blue and magenta curves are associated with degenerate equilibria in the coordinate and = 0 (stable, blue) or = (unstable, magenta). Physically the blue and magenta curves in Fig. 5 represent the situation when the molecules dipole is oriented with the eld (blue) and against it (magenta), while at the same time the molecule is rotating about its own z-axis with direction and angular velocity given by m.

A = {0, } [0, 2). In contrast with the electric eld case, the symmetry of the laser interaction gives only one Vm -m curve for A, Vm (A) = m2 3 . 2I3 (31)

It is straightforward to see that = /2 is a solution of (29a), which after substitution into (29b) gives sin cos (I2 I1 )m2 22 sin cos = 0, I1 cos2 + I2 sin2 (32)

4. E -m Diagrams for Asymmetric Top Molecules in Nonresonant Laser Fields


The eective potential for interaction of a molecule with a nonresonant linearly polarized laser eld ( = 0) is Vm (, ) = m2 2 sin2 sin2 3 ) C3 2(IC 3 cos2 . The relative equilibria are obtained by solving sin cos (I1 cos2 + I2 sin2 I3 )m2 Vm = [(IC3 ) C3 ]2 + V = 0, (29a) (28)

with immediate solutions = 0, /2, , 3/2. The second solution set is therefore B = {/2} {0, /2, , 3/2}. There are two subsets, B1 B and B2 B, given by B1 = {/2} {0, } and B2 = {/2} {/2, 3/2}. For these the Vm -m curves are m2 Vm (B1 ) = , (33a) 2I1 Vm (B2 ) = m2 2 . 2I2 (33b)

Now, = 0, /2, , and 3/2 are particular solutions of Eq. (29b); substituting these values into Eq. (29) and dividing by I3 produces (1 i1 )m2 = 23 I3 [i1 + (1 i1 ) cos2 ]2 , (34a) (1 i2 )m2 = 2(2 3 )I3 [i2 + (1 i2 ) cos2 ]2 , (34b) for = 0, , and = /2, 3/2 respectively, and as before i1 I1 /I3 and i2 I2 /I3 , with i1 > i2 > 1. The nature of the solutions depends on the values of 2 and 3 . For iodobenzene and pyridazine 3 > 2 > 0, since for these molecules 1 < 2 < 3 (cf. Table 1). This is however not always the case: for pyridine with the same axis convention u 1 < 3 < 2 [Hinchlie & Soscn, 1994], which implies 2 > 3 > 0. For a physically reasonable laser intensity 1012 Wcm2 applied to iodobenzene we have 2 /B3 = 284.6 and 3 /B3 = 630.5; the same eld applied to pyridazine produces 2 /B3 = 225.7 and 3 /B3 = 228.9; iodobenzene gives 2 /B3 = 2280.06 and 3 /B3 = 4097.94. These dimensionless ratios are much larger than the corresponding energy ratios for physically relevant values of the interaction with a static electric eld, = 10 and = 20. As we wish to investigate the interesting dynamical regime in which the eects of both elds are of similar magnitude (see next section),

sin cos sin2 (I2 I1 )m2 V Vm = + [(IC3 ) C3 ]2 = 0, (29b) where (IC3 ) C3 is again given by Eq. (25) and V = 22 sin cos sin2 + 23 sin cos , V = 22 sin cos sin2 . (30a) (30b)

From (29)(30) it is seen that = 0, are again simultaneous solutions and the rst solution set is

Classical Mechanics of Dipolar Asymmetric Top Molecules Table 2. Molecule C6 H5 I C4 H4 N2 C6 F5 I /B3 10 20 15 Hamiltonian parameters and asymmetries with respect to y-axis. 3 /B3 63.05 22.88 409.8 2(2 3 )/B3 69.88 0.64 363.58 (3 2 )/(1 2 ) 1.22 0.014 0.797 (I3 I2 )/(I1 I2 ) 6.61 0.045 1.785

1137

2 /B3 28.46 22.56 228.0

we reduce the intensity of the laser by a factor of 10 to obtain the values listed in Table 2. The plot of the RHS and LHS of Eqs. (34) is shown in Fig. 6. The situation is dierent from the static electric eld case. Now the LHS of the equations, the solid horizontal line, moves down as m increases. This line intersects the RHS curve (dashed) at = 0, simultaneously for m values M1 = M2 = 23 I3 1 i1
1/2

Considering only positive values of m, Eqs. (34) can be solved for cos2 to get cos2 = cos2 = m M1 , M1 M 1 m M2 , M2 M 2 (37a)

(37b)

,
1/2

(35a)

2(2 3 )I3 1 i2

(35b)

for = 0, and = /2, 3/2, respectively. The two solutions of each of these equations together with the respective values give the solution sets C for = 0, and D for = /2, 3/2. The Vm -m curves for these solutions are Vm (C) = (M1 M 1 )m2 2[I3 (m M 1 ) + I1 (M1 m)] 3 Vm (D) = m M1 , M1 M 1 (38a)

for = 0, and = /2, 3/2, respectively. As the value of m increases the points of intersection approach the value = /2 symmetrically, i.e. /2 left = right /2. Finally, at m values M 1 = M1 i1 , M 2 = M2 i2 , (36a) (36b)

for = 0, and = /2, 3/2, respectively, the intersection occurs exactly at = /2. For larger values of m there is no solution.
0

(M2 M 2 )m2 2[I3 (m M 2 ) + I2 (M2 m)] 2 + (2 3 ) m M2 , (38b) M2 M 2

0 (1i2) m 2 2(23) I3

(1i1) m 2

23 I3

2(23) I3 i22

23 I3 i12

0.25

0.5 0.75 /

0.25

0.5 0.75 /

Fig. 6. Plots of RHS (dashed), and LHS (solid) of Eqs. (34) for m values at which curves do not intersect. Left panel: Eq. (34a) (i1 = 1.25, (1 i1 )m2 = 5, 23 I3 = 10); right panel: Eq. (34b) (i2 = 1.2, (1 i2 )m2 = 4, 2(2 3 )I3 = 7).

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C. A. Arango & G. S. Ezra


10 8

with m [M1 , M 1 ] and m [M2 , M 2 ] for the rst and second equations respectively. The value of Vm (C) at m = M1 is equal to that of Vm (A) at m = M1 , while its value at m = M 1 is equal to Vm (B1 ) at m = M 1 ; similarly, the value of Vm (D) at m = M2 equals Vm (A) at m = M2 , and at m = M 2 equals Vm (B2 ) at m = M2 . These results indicate that in the E-m diagram the solution set C is a bridge connecting solutions A and B1 . In like fashion the solution set D connects the solutions A and B2 . Finally, the last solution set is obtained from Eqs. (29) after removing all the common factors (I1 cos2 + I2 sin2 I3 )m2 (I1 sin2 cos2 + I2 sin2 sin2 + I3 cos2 )2 22 sin2 + 23 = 0, (39a)

2
6

0 102 E
4 2

4
0

1,1

2
2

1,1
4 0

2,2
20

1,1,1,1

40

60

Fig. 7. E-m diagram for the asymmetric top molecule iodopentauorobenzene in a nonresonant laser eld: 2 /B3 = 228.006 and 3 /B3 = 409.794.

(I2 I1 )m2 (I1 sin2 cos2 + I2 sin2 sin2 + I3 cos2 )2 22 = 0. (39b)

Solutions of these equations for given m are obtained by nding the intersections of the zero contours of the LHS of these equations in the - space. For the case of the laser eld, these equations can be rearranged to get m2 in terms of and m2 = m2 = 2(2 sin 2 3 ) [(IC3 ) C3 ]2 , (40a) I3 I1 cos2 I2 sin2 22 [(IC3 ) C3 ]2 , I1 I2 (40b)

the LHS and RHS of Eq. (43) for the molecules of interest. As condition (42) is not fullled for the molecules considered here, the last solution set is empty, E = . The complete solution for the asymmetric top rotor in a linearly polarized laser eld is then given by SL = A B C D. The Vm -m curves for these solutions in the case of iodopentauorobenzene, iodobenzene and pyridazine are shown in Figs. 79, respectively. In these gures the solution sets are given by dierent types of curves. The solution set A is given by the red curve, B1 by the green curve and B2 by the blue. The bridge solution sets C, connecting A with B1 are magenta; the bridge D, connecting A with B2 , is the cyan curve.

where the denition (25) is used. With the equations written in this form is clear that we must nd such that 22 2(2 sin2 3 ) = . 2 I sin2 I1 I2 I3 I1 cos 2 (41)
102 E

1,1
3

Rearranging and simplifying gives the condition I3 I2 3 = , 1 2 I1 I2 (42)

2
0

4 1,1 1,1,1,1

which can be written in terms of the polarizability I3 I2 3 2 = . 1 2 I1 I2 (43)

1 0

1,1

2,2
20 40 60

In general, this equality is not satised for physical parameter values. For example, Table 2 lists

Fig. 8. E-m diagram for the asymmetric top molecule iodobenzene in a nonresonant laser eld: 2 /B3 = 28.456 and 3 /B3 = 63.05.

Classical Mechanics of Dipolar Asymmetric Top Molecules

1139

0 5

2.5

7.5

10

1,1
4 3 2 1 0 1 2

2 0 2,2 4

10 E

1,1 1,1 1,1,1,1

Fig. 9. 22.88.

E-m diagram for the asymmetric top molecule pyridazine in a nonresonant laser eld: 2 /B3 = 22.56 and 3 /B3 =

For iodopentauorobenzene and iodobenzene there are nine dierent regions delimited by different curve types with their corresponding genera indicated with arrows in Fig. 8. The classically accessible - conguration space for each of these regions is shown in Fig. 10. The simplest region is characterized by genus 0; in this region the molecule is free to move in any possible conguration in - as can be seen in Fig. 10(i). There are two regions with genus 2: one for high energy and large m, the other for low energy and small m. In the high energy region 10(a) shows that the molecule is localized in the equatorial region and the poles are forbidden. The second region with genus 2 is shown in 10(c); in this case the forbidden regions are on the equator with = 0, . For genus 4 there is only one region, shown in panel 10(f); the molecule can access neither

the poles nor the equatorial regions with = 0, . In the case of genus 2,2, panel 10(d), the accessible region is delocalized in and restricted in to a region close, but not on, the poles. Finally, for genus 1,1,1,1 (10(f)) the motion is highly localized near = /4, 3/4 and = /2, 3/2. The fact that both the inertia and polarizability tensors of pyridazine have near-oblate symmetry makes it harder to observe the dierent regions in the E-m diagram, as can be seen from Fig. 9. As I2 I3 and 2 3 , the Vm -m curves for the solution sets A and B2 are very similar. The magenta bridging solution C connecting A and B1 is easily seen, but the cyan D bridge is much harder to see. As for iodopentauorobenzene and iodobenzene, there are nine dierent regions which have the same distribution of genus.

1140

C. A. Arango & G. S. Ezra

2 1.5

1 0.5 0
(a) genus = 2 (b) genus = 1, 1 (c) genus = 2

2 1.5

1 0.5 0
(d) genus = 2, 2 (e) genus = 1, 1, 1, 1 (f) genus = 4

2 1.5

1 0.5 0 0 0.25 0.5 0.75 1 / 0 0.25 0.5 0.75 1 /


(h) genus = 1, 1

0.25 0.5 0.75 1 /


(i) genus = 0

(g) genus = 1, 1

Fig. 10. Classically allowed (red) and forbidden (green) - conguration space and associated genera for the various regions of Figs. 7 and 8.

5. E -m Diagrams for Asymmetric Top Molecules in Collinear Fields


We now consider the rotational dynamics of dipolar asymmetric tops in combined static (Sec. 3) and nonresonant laser (Sec. 4) elds. The polarization of the laser eld is taken to be collinear with the static eld, so that m is a conserved quantity. A related problem has been analyzed by Tatarinov [Arnold et al., 1988; Tatarinov, 1974], who studied the problem of the rotation of a rigid body about a xed point with a potential V = P C3 RCM + (IC3 ) C3 , 2 (44)

In molecular terms, the rst term of the potential (44) corresponds to the interaction of an electric eld along the space-xed z-axis with the dipole moment of the molecule, where the dipole moment vector can point in an arbitrary direction in the molecule-xed frame, R, not only along the molecule xed z-axis as in the case studied here. The second term of (44) has no obvious molecular analog, but the dependence on Euler angles is exactly the same as for the laser interaction. In fact, the potential energy for an asymmetric top in tilted (noncollinear) elds can be written as V = C3 (C3 ) C3 , (45) with the denitions ( sin , 0, cos ), and diag(0, 2 , 3 ). The eective potential for the dipolar asymmetric top in collinear elds, where the dipole moment points along the molecule-xed z-axis, is

where P and are constants, and RCM is the location of the center of mass relative to the xed point. In Tatarinovs work E-m diagrams and genera are obtained for the eective potential.

Classical Mechanics of Dipolar Asymmetric Top Molecules

1141

(cf. Eq. (17)) Vm (, ) = m2 cos 2 sin2 sin2 3 ) C3 2(IC 3 cos .


2

electric eld case, this solution generates two subsets A1 = {0} [0, 2) and A2 = {} [0, 2). The Vm -m curves for these solutions are Vm (A1 ) = Vm (A2 ) = m2 3 , 2I3 m2 + 3 . 2I3 (50a) (50b)

(46)

The relative equilibria are obtained by solving the equations Vm sin cos (I1 + I2 sin I3 = [(IC3 ) C3 ]2 + V = 0, cos2
2

)m2

As for the laser interaction case, Eq. (47b) has solutions = 0, /2, and 3/2, which after substitution into (47a) give cos (1 i1 )m2 = I3 ( + 23 cos ) [i1 + (1 i1 ) cos2 ]2 , (51a) cos (1 i2 )m2 = I3 [ 2(2 3 ) cos ] [i2 + (1 i2 ) cos2 ]2 . (51b) Figures 1113 show plots of the LHS and RHS of Eqs. (51) for iodopentauorobenzene (/B3 = 20, 2 /B3 = 228.006 and 3 /B3 = 409.794), iodobenzene (/B3 = 10, 2 /B3 = 28.456 and 3 /B3 = 63.05) and for pyridazine (/B3 = 20, 2 /B3 = 22.56, and 3 /B3 = 22.88). Figures 11 and 12 show the LHS of (51) for iodopentauorobenzene and iodobenzene (respectively) with m = 0 as a dotted line in both cases; it is clear that on each gure that for m = 0 there is only one intersection at > /2. As the value of m increases, the dashed curve will intersect the solid line at additional points. The RHS of (51a) gives I3 ( + 23 ) at = 0 and I3 ( 23 )

(47a)

sin cos sin2 (I2 I1 )m2 V Vm = = 0, + [(IC3 ) C3 ]2 (47b) with (IC3 ) C3 = I1 sin cos + I2 sin sin (48) + I3 cos2 , and V = sin 22 sin cos sin2 (49a) + 23 sin cos , V = 22 sin cos sin2 . (49b)
2 2 2 2

In both Eqs. (47) the common factor sin gives the simultaneous solution = 0 or , so the rst solution set is A = {0, } [0, 2). As for the static

LHS, RHS

0.25

0.5 /
(a)

0.75

0.25

0.5 /
(b)

0.75

Fig. 11. RHS (solid line) and LHS for m = 20 (dashed line) of Eqs. (51) for iodopentauorobenzene. (a) Eq. (51a); (b) Eq. (51b). Dotted line: m = 0.

1142

C. A. Arango & G. S. Ezra

LHS, RHS

0.25

0.5 /
(a)

0.75

0.25

0.5 /
(b)

0.75

Fig. 12. RHS (solid line) and LHS for m = 10 (dashed line) of Eqs. (51) for iodobenzene. (a) Eq. (51a); (b) Eq. (51b). Dotted line: m = 0.

0 LHS, RHS 0

0.25

0.5 /
(a)

0.75

0.25

0.5 /
(b)

0.75

Fig. 13. RHS (solid line) and LHS for m = 4 (dashed line) of Eqs. (51) for pyridazine. (a) Eq. (51a); (b) Eq. (51b). Dotted line: m = 0.

at = ; for these two molecules in the elds specied above | + 23 | > | 23 |, which implies that the LHS curve intersects the RHS curve rst at = , and then at = 0. For larger m only the leftmost intersection remains with the two intersections with > /2 disappearing simultaneously. This situation is repeated for the second Eq. (51), for which the RHS at = 0, gives I3 [ 2(2 3 )] and I3 [ + 2(2 3 )] respectively; for the elds employed we have for both molecules that | 2(2 3 )| > | + 2(2 3 )|.

For pyridazine the situation is dierent. From Fig. 13(a) it is clear that the RHS curve of (51a) is intersected rst at = , but the two solutions with > /2 will now disappear before the dashed curve intersects the solid curve at = 0. For (51b) there is only one solution, which moves from = 0 to larger values of as the value of m increases. Figures 11 to 13 explain the observed bifurcation structure of the solutions of Eqs. (51). The two panels in Figs. 11 and 12 and panel 13(a) show the existence of a nonbifurcating solution and a pair of

Classical Mechanics of Dipolar Asymmetric Top Molecules

1143

solutions emerging from a saddle-node bifurcation. A global view of the bifurcations is obtained rearranging Eqs. (51) to cos (1 i1 )m2 + I3 ( + 23 cos ) (52a) [i1 + (1 i1 ) cos2 ]2 = 0, 2 cos (1 i2 )m + I3 [ 2(2 3 ) cos ] (52b) [i2 + (1 i2 ) cos2 ]2 = 0, and then plotting the zero contours of the LHS in the -m space. These contours are shown in Fig. 14 for the molecules treated here. The contours indicate that a solution branch for both Eqs. (52) begins at = 0, branching out of the A1 solution. On the
40 30 20 10 0
(a)

other hand, the right branch from the saddle-node pair begins at = , which means that this solution emerges from the A2 solution. The left branch of the saddle-node pair is connected only to its right partner. The last solution set is obtained after removing all common factors in Eqs. (47), and rearranging to obtain m2 as function of and , m2 = 2(2 sin2 3 ) cos [(IC3 ) C3 ]2 , cos I3 I1 cos2 I2 sin2 (53a) 22 [(IC3 ) C3 ]2 , I1 I2 (53b)

m2 =

(b)

40 30 20 10 0
(c) (d)

m m

60 40 20 0 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1

/
(e)

/
(f)

Fig. 14. Zero contours of the LHS of Eqs. (52). Iodobenzene: (a) Eq. (52a), (b) Eq. (52b). Pyridazine: (c) Eq. (52a); (d) Eq. (52b). Iodopentauorobenzene: (e) Eq. (52a), (f) Eq. (52b).

1144

C. A. Arango & G. S. Ezra

0 10 8

10

20

30

40

50

60

1,1 1 2 0 1,1,1,1 3 2 4 1,1

6 4 2 0 2

102 E

1,1
4

1 m
50

10 E

100 150 200 250 10

1,2 1,1,1 1,1,2 2 1,1

14

18

22

Fig. 15. E-m diagram for the dipolar asymmetric top molecule iodopentauorobenzene in collinear static electric and nonresonant laser elds. /B3 = 20, 2 /B3 = 228.006 and 3 /B3 = 409.7945.

with (IC3 ) C3 given by Eq. (48). The solution is obtained by nding all the values of and such that 22 2(2 sin2 3 ) cos = , (54) 2 I sin2 I1 I2 cos I3 I1 cos 2 which can be rearranged and simplied to get 2 cos I1 I3 3 I1 I2 2 = . 2
1

= 0.4896, while for pyridazine there is no solution. The range of m for this solution is obtained from Eq. (53b). The smallest value of m occurs at = /2, 3/2, the largest at = 0, , giving the values Mi = 22 I1 I2 Ii +
1/2

(55)

In terms of the polarizability this gives cos = 22 I1 I3 3 1 I1 I2 2 1 . (56)

2 (I3 Ii ) 2 42

I1 I3 3 I1 I2 2

, (57)

In contrast to Eq. (43), Eq. (56) depends on the elds. For the elds used in iodobenzene we obtain

where i = 1 for = 0, , and i = 2 for = /2, 3/2. A solution of (53) therefore exists for m [M2 , M1 ]. Noting Eqs. (51), and keeping in

Classical Mechanics of Dipolar Asymmetric Top Molecules

1145

2 1.5

1 0.5 0
(a) genus = 2 (b) genus = 1 (c) genus = 1, 1

2 1.5

1 0.5 0
(d) genus = 1, 1 (e) genus = 4 (f) genus = 2

2 1.5

1 0.5 0
(g) genus = 1, 1, 1, 1 (h) genus = 1, 1 (i) genus = 1

2 1.5

1 0.5 0
(j) genus = 3 (k) genus = 1, 1, 1 (l) genus = 1, 2

2 1.5

1 0.5 0 0 0.25 0.5 0.75 1 / 0 0.25 0.5 0.75 1 / 0 0.25 0.5 0.75 1 /
(o) genus = 2

(m) genus = 1, 1, 2

(n) genus = 1, 1, 1, 1

Fig. 16. Classically allowed (red) and forbidden (green) - conguration space and associated genera for the regions in Fig. 15. Genus 0 not included.

1146

C. A. Arango & G. S. Ezra

10

20

30

40

50

60

1,1

102 E

2
0

1,1

m 1,2 1,1,1 1,1 1 1,1,2 1,1,1,1

Fig. 17. E-m diagram for the dipolar asymmetric top molecule iodobenzene in collinear static electric and nonresonant laser elds. /B3 = 10, 2 /B3 = 28.456 and 3 /B3 = 63.05.

mind Eq. (54), we conclude that this solution coincides with the solution of (53a) at m = M2 , and with the solution of (53b) at m = M1 . Using Eqs. (53b) and (57) we obtain sin2 sin2 = M1 m I1 I2 I1 I2 22
1/2

(58)

This equation, together with (55) and (53b) can be substituted into the eective potential (17) to get the Vm -m curve Vm = m M1 2 3 cos2 , 22 I1 I2
1/2

cos (59)

where the last two terms are to be evaluated using Eq. (56). The rst term shows a linear dependence on m. In fact, as seen above, this solution is a bridge between the solutions of (51) at = /2, 3/2 and

= 0, . Although it has not been considered, for negative values of m the solutions are symmetric with respect to reection on the m = 0 line. The E-m diagram for iodopentauorobenzene is shown in Fig. 15. There are 16 dierent regions delimited by the Vm -m curves. In the gure there are two parabolas corresponding to the solution sets A1 (red) and A2 (green), the A1 parabola is always below A2 as should be evident from Eqs. (50). Emerging from the A1 parabola at m 10 there are two curves, one blue the other magenta. These curves correspond to the independent branch solutions of Eq. (52), the blue curve is the solution for = 0, , the magenta one for = /2, 3/2. These two curves intersect near m 50, and near this intersection they are connected by the bridge solution (59) (cyan). Emerging from the A2 curve, near m 10, there are also two curves with the same colors as above; these are the two saddle-node

Classical Mechanics of Dipolar Asymmetric Top Molecules


0 0 5 10 15 20 25 4 5 10 15 20 25

1147
30

1,1 2

2
2

1,1

1
2

0 4 3

2,2

102 E 3

1 0

102 E

2
0

1 2 3

(a)

(b)

Fig. 18. E-m diagram for the dipolar asymmetric top molecule pyridazine in collinear static electric and nonresonant laser elds. (a) /B3 = 20, 2 /B3 = 22.56, and 2 /B3 = 22.88; (b) same electric eld but a laser eld ten times more intense.

bifurcation solutions of Eq. (52) with the blue curve for the = 0, solution and the magenta curve for the = /2, 3/2 solution. The saddle-node bifurcation are observed as cusps near m 40 for the blue curve and m 25 for the cyan curve. The complete E-m diagram is obtained when negative values of m are considered, the diagram is symmetric about the m = 0 axis. For the full diagram the bifurcation partners form smiles that are typical features of this type of system [Tatarinov, 1974] (for analogous structures in the case of diatomic molecules in collinear elds, see [Arango et al., 2004]). The accessible - conguration space for the dierent regions of Fig. 15 is shown in Fig. 16. Comparing with the gure for the laser interaction only (Fig. 10), we see that the genus 2,2, panel 10(d), is not present when the electric eld is turned on; instead, there is a genus 1,2 region, panel 16(l). This indicates that the eect of the electric eld is relatively strong compared to the laser and that it tends to align the molecule dipole along the space xed z-axis. This is also the case for the genus 3 region of Fig. 16(j), which is absent in Fig. 10. Note also that the genus 1,1,1,1 congurations are dierent in both gures. For iodobenzene the E-m diagram, Fig. 17, is simpler than the one for iodopentauorobenzene, Fig. 15. Since the rotational constants for this molecule are considerably larger than those for iodopentauorobenzene, the E-m diagram extends over a smaller energy range. There are only few qualitative changes with respect to Fig. 15. The

most important dierence is that the lower smile lies completely within the 2 region and does not go over to the 1,1 region as for iodopentauorobenzene. This eliminates the lower 2 region observed in the lower panel of Fig. 15 and also the 1,1 region in the same panel. The E-m diagrams for pyridazine are shown in Fig. 18. In panel (a), where /B3 = 20, 2 /B3 = 22.56, and 3 /B3 = 22.88, we obtain a very simple E-m diagram with only six regions. There is only one smile with genre 2 and 3. The second smile does not form since there is only one branch for the = /2, 3/2 solution. In panel (b) we show the E-m diagram for the same value of electric eld but for a laser eld ten times more intense. In this case, the smile has grown bigger, overlapping the regions with genre 1, 2 and 1,1. It is observed that below and above the overlapped regions the genus is the same as for the weaker laser eld case, while inside the smile the genus can vary according to the E-m values.

6. Summary and Conclusions


In this paper we have studied the classical mechanics of rotational motion of dipolar asymmetric top molecules in strong external elds. Static electric elds, linearly polarized nonresonant laser elds, and collinear combinations of the two were investigated. The particular asymmetric top molecules iodobenzene, pyridazine and iodopentauorobenzene have been treated for physically relevant eld strengths.

1148

C. A. Arango & G. S. Ezra

Following Katok [1972] and Tatarinov [1974], we have computed diagrams of relative equlibria in the E-m plane; the relative equilibria correspond physically to periodic motions with the two Euler angles and constant [Katok, 1972; Arnold et al., 1988]. We have also examined the classically allowed - conguration space for dierent regions of the E-m diagrams, and have classied the conguration space topology according to their genus [Arnold et al., 1988]. We anticipate that this classical mechanical investigation will be useful in the dicult problem of assigning quantum mechanical eigenstates and energy levels for asymmetric tops in external elds [Moore et al., 1999; Kanya & Oshima, 2004].

Acknowledgments
We are grateful to Mr. Michael Zukovsky for providing partial translations of references [Katok, 1972] and [Tatarinov, 1974].

References
Arango, C. A., Kennerly, W. W. & Ezra, G. S. [2004] Quantum monodromy for diatomic molecules in combined electrostatic and pulsed nonresonant laser elds, Chem. Phys. Lett. 392, 486492. Arango, C. A. [2005] Ph. D. Thesis, Cornell University. Arango, C. A., Kennerly, W. W. & Ezra, G. S. [2005] Classical and quantum mechanics of diatomic molecules in tilted elds, J. Chem. Phys. 122, 184303. Arnold, V. I. [1978] Mathematical Methods of Classical Mechanics (Springer, Berlin). Arnold, V. I., Kozlov, V. V. & Neishtadt, A. I. [1988] Mathematical Aspects of Classical and Celestial Mechanics (Springer, NY). Artigue, M., Gautheron, V. & Isambert, E. [1986] Bifurcation sets and the topology of integral manifolds in the problem of a heavy rigid body (in French), J. de Mecanique Theorique et Appliquee 5, 429469. Block, P. A., Bohac, E. J. & Miller, R. E. [1992] Spectroscopy of pendular states: The use of molecular complexes in achieving orientation, Phys. Rev. Lett. 68, 13031306. Bolsinov, A. V. & Fomenko, A. T. [2004] Integrable Hamiltonian Systems (CRC Press, Boca Raton). Broucke, R. A. [1993] On the use of Poincar surfaces e of section in rigid-body motion, J. Astronaut. Sci. 41, 593601. Bulthuis, J., Moller, J. & Loesch, H. J. [1997] Brute force orientation of asymmetric top molecules, J. Phys. Chem. A 101, 76847690.

Bunker, P. R. & Jensen, P. [1998] Molecular Symmetry and Spectroscopy, 2nd edition (NRC Research Press, Ottawa). Casimir, H. B. G. [1931] Rotation of a Rigid Body in Quantum Mechanics (Wolters, The Hague). Chavoya-Aceves, O. & Pina, E. [1989] Symmetry lines of the dynamics of a heavy rigid body with a xed point, Il. Nuov. Cim. B 103, 369387. Child, M. S. [1991] Semiclassical Mechanics with Molecular Applications (Oxford University Press, NY). Cooper, C. D. & Child, M. S. [2005] Quantum level structures at a Fermi resonance with angular momentum: Classical periodic orbits, catastrophe maps and quantum monodromy, Phys. Chem. Chem. Phys. 7, 27312739. Cushman, R. H. & Bates, L. M. [1997] Global Aspects of Classically Integrable Systems (Birkhauser, Basel). Cushman, R. H. [2005] No polar coordinates, eds. Montaldi, J. & Ratiu, T., Geometric Mechanics and Symmetry: The Peyresq Lectures (Cambridge, Cambridge), pp. 211301. Deprit, A. [1967] Free rotation of a rigid body studied in the phase plane, Am. J. Phys. 35, 424428. Deprit, A. & Elipe, A. [1993] Complete reduction of the EulerPoinsot problem, J. Astron. Sci. 41, 603628. Galgani, L., Giorgilli, A. & Strelcyn, J. M. [1981] Chaotic motions and transition to stochasticity in the classical problem of the heavy rigid body with a xed point, Il Nuov. Cim. B 61, 120. Gashenenko, I. N. & Richter, P. H. [2004] Enveloping surfaces and admissible velocities of heavy rigid bodies, Int. J. Bifurcation and Chaos 14, 25252553. Goldstein, H., Poole, C. & Safko, J. [2002] Classical Mechanics, 3rd edition (Addison-Wesley, San Francisco). Grozdanov, T. P. & McCarroll, R. [1996] Level statistics for asymmetric-top rotors in strong electric elds, Z. Phys. D 38, 4549. Gutzwiller, M. C. [1990] Chaos in Classical and Quantum Mechanics (Springer-Verlag, NY). Harter, W. G. [1988] Computer graphical and semiclassical approaches to molecular rotations and vibrations, Comp. Phys. Rep. 8, 319394. Hinchlie, A. & Soscn, H. J. [1994] Ab initio studies u of the dipole polarizabilities of conjugated molecules. Part 2. Monocyclic azines, J. Mol. Struct.-Theochem 304, 109120. Iacob, A. [1971] Invariant manifolds in the motion of a rigid body about a xed point, Rev. Roum. Math. Pures et Appl. XVI, 14971521. Innes, K. K., Ross, I. G. & Moodmaw, W. R. [1988] Electronic states of Azabenzenes and Azanaphthalenes: A revised and extended critical review, J. Mol. Spectrosc. 132, 492544. Kanya, R. & Oshima, Y. [2004] Pendular-limit representation of energy levels and spectra of symmetric

Classical Mechanics of Dipolar Asymmetric Top Molecules

1149

and asymmetric-top molecules, Phys. Rev. A 70, 013403. Katok, S. B. [1972] Bifurcation sets and integral manifolds in the rigid body problem (in Russian), Usp. Mat. Nauk. 27, 126133. Kellman, M. E. [1995] Algebraic methods in spectroscopy, Ann. Rev. Phys. Chem. 46, 395421. Klein, F. & Sommerfeld, A. [1965] Uber die Theorie des Kreisels (Teubner, Stuttgart). Kozin, I. N., Roberts, R. M. & Tennyson, J. [2000] Relative equilibria of D2 H+ and H2 D+ , Mol. Phys. 98, 295307. Kozin, I. N. & Roberts, R. M. [2003] Monodromy in the spectrum of a rigid symmetric top molecule in an electric eld, J. Chem. Phys. 118, 1052310533. Kroto, H. W. [1992] Molecular Rotation Spectra (Dover, NY). Lewis, D., Ratiu, T., Simo, J. C. & Marsden, J. E. [1992] The heavy top. A geometric treatment, Nonlinearity 5, 148. Li, H. Z., Franks, K. J., Hanson, R. J. & Kong, W. [1998] Brute force orientation and alignment of pyridazine probed by resonantly enhanced multiphoton ionization, J. Phys. Chem. A 102, 80848090. Marsden, J. E. [1992] Lectures on Mechanics (Cambridge University Press, Cambridge). Marsden, J. E. & Ratiu, T. S. [1999] Introduction to Mechanics and Symmetry (Springer-Verlag, NY). Montaldi, J. A. & Roberts, R. M. [1999] Relative equilibria of molecules, J. Nonlin. Sci. 9, 5388. Moore, D. T., Oudejans, L. & Miller, R. E. [1999] Pendular state spectroscopy of an asymmetric top: Parallel and perpendicular bands of acetylene-HF, J. Chem. Phys. 110, 197208. Oshemkov, A. A. [1991] Fomenko invariants for the main integrable cases of the rigid body motion equations, Adv. Sov. Math. 6, 67146. Perelemov, A. M. [2002] Kovalevskaya top: An elementary approach, Theor. Math. Phys. 131, 612620.

Peronne, E., Poulsen, M. D., Bisgaard, C. Z., Stapelfeldt, H. & Seideman, T. [2003] Nonadiabatic alignment of asymmetric top molecules: Field-free alignment of iodobenzene, Phys. Rev. Lett. 91, 043003. Peronne, E., Poulsen, M. D., Stapelfeldt, H., Bisgaard, C. Z., Hamilton, E. & Seideman, T. [2004] Nonadiabatic laser-induced alignment of iodobenzene molecules, Phys. Rev. A 70, 063410. Poulsen, M. D., Peronne, E., Stapelfeldt, H., Bisgaard, C. Z., Viftrup, S. S., Hamilton, E. & Seideman, T. [2004] Nonadiabatic alignment of asymmetric top molecules: Rotational revivals, J. Chem. Phys. 121, 783791. Rose, J. P. & Kellman, M. E. [2000] Spectral patterns of chaotic acetylene, J. Phys. Chem. A 104, 10471 10481. Seideman, T. & Hamilton, E. [2005] Nonadiabatic alignment by intense pulses. Concepts, theory, and directions, Adv. At. Mol. Opt. Phys. 52, 289329. Smale, S. [1970] Topology and mechanics. I., Inv. Math. 10, 305331. Stapelfeldt, H. & Seideman, T. [2003] Colloquium: Aligning molecules with strong laser pulses, Rev. Mod. Phys. 75, 543557. Tatarinov, Ya. V. [1973] Phase topology of compact congurations with symmetry (in Russian), Vestnik. Moskov. Univ. 28, 7077. Tatarinov, Ya. V. [1974] Portraits of the classical integrals of the problem of rotation of a rigid body about a xed point (in Russian), Vestnik. Moskov. Univ. 29, 99105. Townes, C. H. & Schawlow, A. L. [1975] Microwave Spectroscopy (Dover, NY). Wiesenfeld, L., Faure, A. & Johann, T. [2003] Rotational transition states: Relative equilibrium points in inelastic molecular collisions, J. Phys. B 36, 1319 1335. Zare, R. N. [1988] Angular Momentum (WileyInterscience, NY).