PAPER

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Energy level promotion in the correlation from the tunnelling-doubled harmonic oscillator to the bi-rotor: application to internal rotation in molecules
Stephen C. Rossab and Koichi M. T. Yamadacd
Received 12th July 2007, Accepted 7th September 2007 First published as an Advance Article on the web 20th September 2007 DOI: 10.1039/b710691b A surprisingly rich variety of phenomena are revealed in the energy level correlation between the limits of a tunnelling doubled harmonic oscillator and a bi-rotor. Some levels are found to have their vibrational quantum number promoted upon removal of the barrier to rotation, other levels, which we dub invariant, are found to be completely independent of the barrier, while yet other levels exhibit a smooth transition between these limits. The general nature of these features can be understood in terms of the dierent degeneracies of the limiting cases. The elucidation of these eects aids the understanding of the rotationalvibrational energy levels of molecules having two internal rotor moieties.

I.

Introduction

A variety of simple solutions of the Schrodinger equation are valuable as textbook examples and also as the basis for understanding more complicated systems. The hydrogen atom, the particle-in-a-box, and the harmonic oscillator are prime examples. Less commonly cited is the free rotor. The free rotor problem is analogous to that of a particle-in-a-box, but with periodic boundary conditions. These result in qualitative dierences in the solutions of the Schrodinger equation. Although the energy level spectrum in both systems is of the form E p n2, the lowest level for the free rotor is a unique level of the form f constant. All higher levels have sinusoidal wavefunctions, as do all the levels of the particle-in-a-box problem, but in the free rotor case these levels are doubly degenerate, consisting of 901 phase-shifted pairs. As we will show below, this dierence in degeneracies leads to unusual features in the energy level spectrum of molecules possessing two internal rotor moieties. Increasing the dimensionality of these systems enriches their physical features. For example, angular momentum appears naturally in a two-dimensional isotropic harmonic oscillator. The case of a double free rotor is the analogous extension of the free rotor to a higher dimensionality and forms the unhindered limiting case for internal rotation seen in many classes of molecules. Moieties exhibiting internal rotation can be symmetric tops (as in ethane, C2H6) or consist of a single atom as in the systems we consider here, exemplied by HSSH,

shown in Fig. 1. We concentrate on the case of equivalent rotor moieties, briey mentioning the non-equivalent case at the end. Internal rotation can be hindered to a greater or lesser extent. The energy level patterns vary dramatically with the potential energy barrier to internal rotation, H, correlating with two limiting cases: a tunnelling-doubled harmonic oscillator within the limit of a high barrier and a pair of free rotors within the limit of no barrier. More physical intermediate cases have presented a continuing challenge in molecular physics. The assignment of molecular rotationalvibrational energy levels, both in experiment and in theoretical calculations, is not trivial. For example, in the case of non-equivalent rotors, recourse has been made to the extended group method of Hougen and DeKoven.1 Their method could be

Department of Physics and Centre for Laser, Atomic, and Molecular Sciences, University of New Brunswick, P. O. Box 4400, Fredericton, New Brunswick, Canada E3B 5A3 b Infrared Free Electron Laser Research Center, Tokyo University of Science, 2641 Yamazaki, Noda, Chiba, 278-8510, Japan c National Institute of Advanced Industrial Science and Technology (AIST), EMTech, AIST Tsukuba West, Onogawa 16-1, Tsukuba, 305-8569, Japan d A&A Laboratories, Sengataki Naka-ku 523-1, Karuizawa, Nagano, 389-0111, Japan

Fig. 1 Schematic diagram of HSSH type of molecules. The signed quantum numbers ni, i 1, 2, are used for the internal rotation of each end of the molecule. Unlike what is shown here, the GSRB calculations have the x-axis xed along one of the SH bonds.

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dubbed the rational approximation group theory technique relying, as it does, on a rational approximation to the ratio of the moments of inertia of the rotor moieties. Here we wish to proceed more directly to an understanding of the energy structure and wavefunction form for such molecules. In 1928 Wigner and Witmer2 and Mulliken,3 building on work of Hund,46 showed that consideration of the correlation between the limit of atomic electronic states and the limit of molecular electronic states is a powerful tool for understanding the electronic structure of diatomic molecules. Here we show that consideration of the correlation between the limit of an unhindered bi-rotor (i.e. one with no barrier to internal rotation) and that of a tunnelling-doubled harmonic oscillator with a strong barrier to internal rotation is also very useful. In the correlation we nd invariant levels, i.e. levels unaected by the barrier height, along with levels that present a feature analogous to the promotion of quantum orbitals that can occur as two atoms, brought together to form a diatomic molecule.3 Combined with other levels that behave more normally, this correlation provides a coherent picture of the otherwise complicated energy level structure in molecules possessing two internal rotor moieties and an intermediate degree of hindering. II. Correlation diagram obtained from GSRB

We explore this correlation using the generalised semirigid bender (GSRB) program. The GSRB was recently used in the elucidation of the nature of quantum monodromy in quasilinear molecules7,8 and is an extension of the semirigid bender model of Bunker and Landsberg9 which is itself an extension of the HougenBunkerJohns (HBJ) Hamiltonian.10 The HBJ approach treats the rotation and one large-amplitude vibration of the molecule by introducing a four-dimensional generalisation of the moment of inertia matrix which depends on the coordinate for the large-amplitude motion r. We choose r as the angle between the two HSS moieties. One molecular

reference axis is xed in the plane of one of the HSS moieties of the molecule, leading to strong coupling of the vibrational rotational basis and requiring the use of a somewhat larger basis set. However, this choice also means that increasing r from 0 to 2p brings the system identically back to its initial situation at r 0. (If the reference axis is xed in the bi-rotor bisector plane then r would have to increase to 4p to bring the reference axes and the molecule back to the initial situation, giving rise to unphysical levels that must later be discarded.11) The gures below give GSRB results for a molecule with geometry and masses akin to those of HSSH. For a conceptual understanding of the GSRB results we take a simplied view of the two limits of the bi-rotor system. First we consider the free rotor (unhindered, or H 0) case. As shown in Fig. 2 we use ni, i 1, 2, as signed quantum numbers for the internal rotation of each end of the molecule, with the sign indicating the sense of the rotation. Such internal rotation gives rise to a component, k, of angular momentum along the z-axis, k n1 n2. If n1 a n2 the molecule is internally twisted and the resulting signed torsional quantum number is n n1 n2. Molecules of the type HSSH typically have potential energy minima at two skew angles with two potential energy barriers to twisting (properly called internal rotation) when the SH moieties are parallel or antiparallel. For simplicity of illustration, we consider the case of equal potential energy barriers at 90 and 2701. In a molecule with identical rotor moieties and H 0 the energy due to internal rotation takes the particularly simple form of a sum of squares, E An2 Ak2 2An2 n2 2Aw: 1 2 2:1

Here A is the inertial constant about the z-axis of the full molecule and w n12 n22. The squares in this expression mean that we can use the unsigned quantum numbers Ni |ni | to label the bi-rotor energy states as [N1, N2]. For our prototype HSSH molecule these bi-rotor energy state labels

Fig. 2 The correlation of energy levels for J 3 from the free rotor limit (H 0 cm1) to the deeply hindered case, plotted relative to the energy of the lowest J 0 level. The broad, slightly curved, line is the potential energy barrier. Bi-rotor state labels [N1, N2] are given at the left, tunnelling doubled harmonic oscillator labels v are given at the right in (b). For each K level the approximate degeneracy (on the scale of this gure) is given in parentheses. The quadruply degenerate K 3 level divides into two pairs of approximately degenerate levels. In (b) barrier-invariant levels are labelled invariant while promoted levels are labelled promotion.

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are shown in the left of each panel of Fig. 2. We label the individual substates of each bi-rotor energy state using signed quantum numbers as (n1, n2), where the rst entry represents the signed angular momentum quantum number of one rotor moiety, and the second that of the other rotor moiety. As for the two-dimensional harmonic oscillator, bi-rotor states can be degenerate. With identical rotor moieties a bi-rotor state [N1, N2] of given energy can be formed in eight distinct ways: (N1, N2), (N1, 8N2), and the same with N1 and N2 switched. However, if N1 N2, or if one of them is 0, there are only four distinct combinations, if both are 0 there is only one combination. Thus, at a particular energy, we either have eight-fold degeneracy, four-fold degeneracy, or no degeneracy. For higher levels accidental degeneracies, such as 02 52 w 32 42 and 12 72 w 52 52, give rise to nonequivalent polyads, further enriching the energy level structure. The picture just presented is somewhat modied when we account for the energy of the end-over-end rotation of the molecule, not just the component along the z-axis. The total angular momentum quantum number, J, must be at least K |k| |n1 n2 |, leading to the relationship between the internal rotation quantum state and the allowed rotation levels J Z K |n1 n2 |. This is analogous to the link between the possible values of the angular momentum and the vibrational quantum numbers in the case of the two-dimensional harmonic oscillator. End-over-end rotation increases the level energy given in eqn (2.1) to give E 2Aw BJJ 1 K 2 ; 2:2

III. Degeneracy, invariance, and promotion

On the scale of Fig. 2 most of the levels shown are degenerate with the degree of degeneracy indicated in parentheses. For the K 3 level shown here we write the degeneracy as (2 2) since splitting into two pairs of levels is just becoming visible. This breaking of the degeneracy is briey discussed further below. For even-K in the free rotor limit the lowest bi-rotor state is [K/2, K/2]. For a particular K this level only has 2-fold degeneracy: (K/2, K/2) and (K/2, K/2), (so only 1-fold if K 0). In the hindered limit the degeneracy must be 4-fold (2-fold if K 0) due to the K-doubling (i.e. k K and K both exist) combined with the tunnelling doubling. As the potential energy barrier is lowered this means that there are twice as many sub-levels for each even-K than allowed in the free rotor limit. Therefore, as clearly visible in Fig. 2b, half of the sub-levels for each even-K are promoted as the barrier drops to zero, analogous to the promotion of orbitals that can occur as two atoms are brought together to form a diatomic molecule.3 The behaviour of the other half of the sub-levels, those that correlate to the free rotor state [K/2, K/2], is completely dierent and initially surprising: in Fig. 2b these sub-levels are seen to be completely barrier-invariant. These sub-levels are (K/2, K/2) and (K/2, K/2) for which the torsional quantum number is n n1 n2 0. This means that the two moieties are co-rotating and the entire molecule is simply rotating around the z-axis, which is not aected by the torsional potential energy function. For odd-K the lowest state in the free rotor limit is [(K 1)/2, (K 1)/2], which for each K has the same 4-fold degeneracy as the correlating hindered limit. Thus, as visible in Fig. 2b, the odd-K levels more-or-less stick together as the potential energy barrier is swept from one limit to the other. Fig. 3, plotted relative to the potential energy minimum, illustrates how this quantum level re-ordering plays out in terms of wavefunctions. Fig. 3a shows the energy correlation for the lowest K 0 levels. The quantum labels for the free and strongly hindered limits are given at the left and right of the graph, respectively. Fig. 3b and c show the GSRB torsional energies and their wavefunctions for K 0 for selected potential energy barriers. Fig. 3b includes the potential energy function, whereas for clarity of labelling Fig. 3c does not. In both panels the level energies are shown by horizontal lines, connected by diagonal lines for dierent values of H. Note that the horizontal line labelled |[0, 0]i for H 0 is the wavefunction of the lowest level which has an approximately constant value of E1/O2p. Levels and wavefunctions correlating in the high barrier limit to symmetric harmonic oscillator wavefunction combinations are show with solid lines, while those correlating to antisymmetric wavefunctions are shown by dashed lines. Following the progression from left to right in Fig. 3b and c, we see that with increasing barrier (or, equivalently, increasing well depth) the lowest level concentrates in the potential well between the barriers, nally taking the form of a symmetric combination of v 0 harmonic oscillator wavefunctions within the limit of the high barrier. Within this limit the antisymmetric combination must also appear. Since the lowest free rotor level [0, 0] K 0 is single, the antisymmetric level 0
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where B is the eective inertial constant for rotation perpendicular to the z-axis. The K2 term breaks a given [N1, N2] state into separate K levels, thereby reducing the degeneracy, as seen on the left part of Fig. 2a and b. The other bi-rotor limit is the case of high barrier. The rightmost panel of Fig. 3b shows that within this limit there are two, nearly harmonic, equivalent potential energy wells separated by a cyclic barrier. We therefore expect almost degenerate symmetric and antisymmetric combinations of harmonic oscillator wavefunctions for each well. These are the tunnelling doublet states which we label with the vibrational quantum number of the wavefunction in one well, v, along with a or superscript for the symmetric and antisymmetric combinations, respectively, that is as v. We write the corresponding wavefunctions as |vi. With v dened in this manner the energy levels within this limit are, approximately, E v 1=2w: h 2:3

Fig. 2 shows the GSRB calculated energies as a function of barrier height for J 3. All quantities in this gure are plotted relative to the energy of the J 0 level correlating with the [0, 0] bi-rotor level. Thus the barrier energy, H, slopes upward in a curve rather than in a straight line. The energy levels are labelled on the left by the appropriate bi-rotor label, [N1, N2], and in the right part of Fig. 2b by the appropriate tunnelling doubled harmonic oscillator label v. Each level is also labelled with K, the unsigned quantum number for the projection of the angular momentum along the molecular z-axis.
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Fig. 3 (a) Correlation of K 0 energy levels between the unhindered bi-rotor limit (left) and the tunnelling doubled harmonic limit (right). Unlike Fig. 2, these are plotted relative to the potential minimum. Bi-rotor state labels [N1, N2] are given on the left, tunnelling doubled harmonic oscillator labels v are given on the right (b) (which also includes the potential energy function), and (c) show the GSRB torsional energies (horizontal lines) and their wavefunctions for K 0 for several potential energy barriers. The horizontal line labelled |[0, 0]i for H 0 in (c) is the wavefunction of the lowest level which has an almost constant value of E1/O2p. Level energies for dierent barrier values are connected by diagonal lines. Levels correlating to symmetric harmonic oscillator wavefunction combinations in the high barrier limit are shown with solid lines, as are their wavefunctions, those correlating to antisymmetric combinations are shown with dashed lines.

must come from above, and it is one of the degenerate pairs of rst excited free rotor wavefunctions |[1,1]i that do this. The other wavefunction of the excited pair begins to acquire a dimple, eventually taking the form of a symmetric combination of v 1 harmonic oscillator wavefunctions, correlating to 11 within the limit of the high barrier. This borrowing from above continues up the energy level stack and is a direct consequence of the uniqueness of the lowest free rotor level. Viewed in the reverse direction, from high to low barrier, we say that half of each degenerate hindered-rotor level is promoted to a higher vibrational level as the barrier is removed, exactly as expected from the discussion of degeneracy given above. In this rich variety of behaviours: promotion or invariance for even-K versus regular change for odd-K, we nd an
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explanation for the observed staggering of energy splittings in HSSH type molecules. Experimentally even-K levels are observed to have larger splittings than odd-K levels.12 This we now see is due to the wider separation between promoted and invariant sub-levels compared to the odd-K sub-levels which move as a group between the two limiting cases.

IV. Discussion
The discussion above has been somewhat simplied for clarity. Thus we neglected the eects of vibrational averaging over dierent geometries and of the dependence of the GSRB moment of inertia tensor on the angle r. These lead to splitting of the degeneracy, even in the case of zero barrier. Thus the degeneracy labels in Fig. 2 are approximations. It is important
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to note that these eects are accounted for in the GSRB calclations. The calculated results presented here represent a relatively simple situation as they are restricted to a molecule having identical rotor moieties, potential energy minima at exactly 901 relative orientations of these moieties, and equal potential energy barriers. However, the GSRB program handles the general case. For example, changing the torsional angle of the potential energy minima from 90 and 2701 leads to greater eective asymmetry in the molecule with the consequence that various K sub-levels shown as approximately degenerate in the scale of Fig. 2 separate further than they do there. In the case of non-equivalent rotor moieties eqn (2.1) is no longer valid. In this case the energy of the state [N1, N2] is not equal to that of [N2, N1] and the staggering pattern of K-splittings is then dierent than it is for HSSH, although still present and easily understandable by examining the appropriate correlation diagram. For example, in the case of DSSH, for J 6 it is the levels with K 0, 3, and 6 that exhibit approximate invariance and promotion and which have wider splittings. In general cases invariance and promotion would show up at non-integer values of K. Since such levels do not exist the eects are spread over the levels with an adjacent integer K, leading to a more complicated but now still understandable energy level pattern. We conclude that the features identied in the present work appear in the more general case, albeit with some modication in detail. Promotion and degeneracy continue to play a role, and examination of a correlation diagram such as Fig. 2 allows a unied and qualitative understanding of the energy level pattern in molecules possessing two internal rotors. This is particularly important for the otherwise dicult intermediate cases of internal molecular rotation encountered experimen-

tally. In addition, the GSRB program can perform quantitative calculations and should allow the determination of the potential energy function and the torsional dynamics (how the bond lengths and angles depend on r) by least-squares tting to experimental data.

Acknowledgements
We acknowledge the support of the Natural Sciences and Engineering Research Council of Canada and the practical and friendly assistance of the sta of the AIC (AIST) in Tsukuba.

References
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