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# Analyzing intramolecular vibrational energy redistribution via the overlap intensity-level velocity correlator

## I Introduction

The nature of the dynamics of a molecule in a highly excited rovibrational state has been a subject of considerable study and debate for a number of yearsrev . Deciding the fate of a localized excitation in a molecule at high energies in terms of the time scales, pathways, and final destination has posed a significant challenge for experimentalistsrev1 ; rev3 ; rev4 ; rev5 ; rev6 ; rev7 ; rev8  and theoristsrev ; rev2 ; rev9 ; rev10  alike. Intramolecular vibrational energy redistribution (IVR), as it has been called, is perhaps one of the most important phenomenon in chemical physics. It is now well established that IVR plays a crucial role in our understanding of reaction rate theories and the ability to effect mode specific chemistry. The advent of modern high resolution spectroscopic techniquesrev3 ; rev6 ; rev7 ; rev8  has led to a fairly detailed study of a number of molecules in highly excited energy regions. Such beautiful and precise studies have demonstrated the richness and complexity of IVR in various molecules and are an essential step towards realizing the goal of quantum control of chemical reactions.

As a result of a number of experimental and theoretical studies, a standard paradigm for IVR called the tier model has evolvedrev ; rev1 ; rev2 ; rev3 ; rev4 ; rev5 ; rev6 ; rev7 ; rev8 . In this model an optically bright state is coupled to a bath of dark states in a hierarchical fashion. In a typical experimental situation, the bright state corresponds to the eigenstate of the zeroth-order molecular Hamiltonian $`H_0`$ which carries almost all of the oscillator strength. The form for this zeroth-order Hamiltonian involves the rigid rotor-harmonic oscillator part corrected perturbatively for nonresonant anharmonic interactions. The rest of the eigenstates of $`H_0`$ having negligible oscillator strength are termed dark states. At low energies the excitation is localized since the bright state is not coupled or very weakly coupled to the dark states. However, at higher energies the bright state is coupled to the dark states by various perturbations $`V_j`$ which include anharmonic resonances, coriolis and centrifugal couplings. These off-diagonal couplings are responsible for the flow of energy from the initial bright state into the various dark states. The system is more appropriately described by the Hamiltonian $`H_0+_j\tau _jV_j`$ in such energy regimes with the $`\tau _j`$ denoting the strengths of the perturbations $`V_j`$. Thus, the experimental signature of IVR in the frequency domain is revealed as a fragmentation of a single rovibrational transition into a multiplet. Ample evidence exists in the literature indicating that the bright state is not coupled democratically to all of the possible dark states. Instead there is a small subset of the dark states, termed as belonging to the first tier, that strongly couple to the bright state. This first tier of states controls the initial stages of the energy flow and hence corresponds to the shortest timescale in the system dynamics. They are coupled to another set of dark states forming the second tier and giving rise to a second, longer timescale for energy flow. This pattern of the couplings leads to a hierarchical tier-model description of IVR in isolated molecules. For instance, Callegari et. al. have recently observedbenzene  seven different timescales ranging from 100 fs to 2 ns for IVR from the first CH strech overtone of the benzene molecule.

One of the key issues in IVR studies is the nature of the states that make up the various tiers. Identifying the nature of the dark states is an important first step towards the ultimate goal of determining the tier by tier classification of the states, i.e. deciding the potential IVR pathways from the bright state of interest. Theoretically, in order to know the destination of the initial excitation, it is necessary to identify the terms in the molecular Hamiltonian which are responsible for the coupling between the bright and the dark states. A molecular Hamiltonian is needed, but it is well known that determining the ab initio potential surface to sufficient accuracy is not routine except for small molecules. In order to make progress, a slightly different viewpoint has been adopted in the literature. Starting from the experimentally measured levels spanning the energy range of interest, an effective spectroscopic Hamiltonian is determined which reproduces the levels to a certain accuracy. The anticipation is that such an effective Hamiltonian can be used to study the eigenstates and dynamics of the system in the given energy range. Effective spectroscopic Hamiltonians have been determinedhcp1 ; hocl1 ; ethy ; water ; qu1 ; qu2  for a number of molecules like phosphaethynehcp1  (HCP), hypocholorous acidhocl1  (HOCl), acetyleneethy , and waterwater  to quote a few. The effective Hamiltonians typically involve anharmonic resonances which couple the zeroth-order modes of $`H_0`$. Fairly detailed quantum, classical, and semiclassical studies using the effective Hamiltonians have providedhcp1 ; hocl1 ; ethy1 ; water1 ; qs0 ; qs1 ; qs2 ; qs3 ; qs4 ; qs5 ; qs6 ; qs7 ; qs8  considerable insights into the nature of the eigenstates and IVR. For example, the genesis of the isomerization stateshcp1  in HCP and determiningethy1  the counter-rotation modes involving the Hydrogens in C2H2 have all been possible due to such detailed quantum-classical correspondence studies. However, most of these detailed studies are restricted to two dimensional or quasi-two degree-of-freedom systems with little3dwork  or no work on three or higher degree of freedom systems. The reasons for this are many fold and mainly have to do with the fact that correlating quantum eigenstates with classical Poincaré surface of sections, periodic orbits, and Husimihusimi  distribution functions from a phase space perspective is considerably harder for three or more degrees. From an eigenstate perspective, it is clear that identifying relevant couplings in a particular energy range is intimately linked to the possible dynamical assignments of the highly excited eigenstates.

In principle, the required information is buried in the splitting pattern as revealed by a eigenstate resolved spectrum. However, in practice the task of analyzing the splittings in order to determine even the nature of the first tier states is nontrivial. In the happy instances when the bright state is perturbed strongly by a single state, there is a two-state scenario, and theoretical as well as experimental techniques can be brought to bear on the problem. Examples of such two state interactions can be found in the experiments by Boyarkin et. al. on the IVR from O-H stretch overtones in methanolmeth  and Mork et. al. on vibrational mode-coupling in 1,2-difluoroethanemork . Various level selection schemes have been proposedtier1 ; tier2 ; tier3 ; tier4  which allow one to determine the dark states tier structure for a specific bright state of interest. However, as soon as the two state picture gets superseded by a situation where two or more states are coupled strongly to the bright state the analysis is quite involved. A previous theoretical studywatercpl  on the assignment of the highly excited vibrational states of H2O provides a good example of the complications that can potentially arise even in a three-state situation. The complexity of the analysis escalates with increasing density of states and with the presence of nonperturbative quantum effects like dynamicaldyntunn  and chaos-assisted tunnelingchaotunn . It is important to note that recent high resolution experiments using double resonance methodsirir1 ; irir2 ; eros ; eros2  have made it possible to elucidate the nature of the dark states that are coupled to the zeroth-order bright state. Analyzing the double resonance spectra with the technique of the hierarchical tree analysishier1 ; hier2 , introduced by Davis, and the traditional perturbation methods yield important information about the nature of the dark states and the number of tiers participating in the IVR process. In addition, with considerable effort, it is possible to identify the nature of the coupling i.e., anharmonic or coriolis, between the bright state and the first tier statespropyne . Such an approach leads to a certain amount of insight on the important energy flow pathways from a bright state of interest. Nevertheless, identifying a dominant anharmonic or coriolis perturbation among the various possibilities is still an important and difficult problem.

One of the principal aims of this work is to develop a systematic and experimentally accessible method to decide the relative importance of perturbations in a given energy range. It is also desirable to be able to analyze multidimensional effective spectroscopic Hamiltonians in terms of the classical-quantum correspondence without explicit determination of the periodic orbits. In particular, this work begins to provide a theoretical foundation for the central feature that has emerged from the various experimental and theoretical studies of IVR, i.e. the strong correlation between the eigenvalue and eigenfunction fluctuation measures. Manifestations of such correlations are evident in the hierarchical tier structure, power law decay of the survival probability at intermediate timesrev5 ; woly ; sri ; grueb1 , nonergodic energy flow even in large molecules like Benzenebenzene , and localized eigenstates at fairly high energieswater1 ; ethy1 ; grueb2 . The hierarchical tree analysishier1  was one of the first attempts to take into account this correlation in a systematic manner. More recently, Gruebele has addressed the problem by introducingmfd1  the matrix fluctuation-dissipation (MFD) method. Apart from having numerical advantages, the MFD theorem explicitly highlights the correlation between spectral intensities and eigenvalues. Perhaps more relevant in the context of the present work is the important role played by the parametric variation of the eigenvalues with changing bright-dark coupling strengthmfd2 . Interestingly, many years ago Weissman and Jortner discoveredweijort  a remarkable correlation between the topological features of the quantum Poincaré maps (basically the Husimi distribution function) and the sensitivity of the energy levels to the strength of the nonlinear coupling. In what follows, it will become clear that the current work provides a quantitative and qualitative basis for the observations by Weissman and Jortner.

Independently, considerable efforts have been made by the quantum chaos community towards understanding the origins and mechanisms of eigenstate localization in fully chaotic systemsradons ; billiard ; bsep ; cantor ; diffus ; scar ; bog ; kaplan . In this extreme limit, quantum ergodicity is conjectured to generate results consistent with random matrix theories (RMT)bgs ; stechel . A key feature of RMT is the complete absence of correlations between eigenvalue and eigenfunction properties. Recently one of us (ST)stprl  introduced a sensitive measure of eigenstate localization which is based on correlations between intensities and eigenlevel velocities. Eigenlevel velocities are more properly defined as the slopes of the level curves generated by changes in some system parameter. It was demonstrated in a series of papersstprl ; cllt ; lct  that this intensity-level velocity correlation function provided an ideal measure to explore the systematic deviations from the predictions of RMTrmt  due to localization. For a detailed introduction to the localization aspects and as to how it relates to the deviations from RMT predictions we refer the reader to Ref. cllt, . An attractive feature of a measure based on the level velocities stems from recent works demonstrating the fingerprints of a nonlinear resonance in the level dynamicsfinger  and the ability of the level velocities to distinguish between different regions of the phase spaceparisri . In a more general context, the current and recent workscllt  provide a natural framework to analyze the spectroscopy of molecules in external fields. Recent examples of such “parametric spectroscopy” experiments include the molecular Stark effect studyeros ; eros2  on 2-propyn-1-ol and the Laser Induced Fluorescence (LIF) study on NO2 in an external magnetic fieldnygard . These observations provide us with a strong motivation to explore the potential usefulness of the correlation measure in the study of IVR.

The paper is organized as follows. A brief introduction to the intensity-level velocity correlation function is provided in section II. The main results for the case when the underlying classical dynamics is fully chaotic, and the RMT expectations are briefly discussed. In section III, the semiclassical theory for the correlation function is constructed for classically integrable systems. Understanding the integrable case is a necessary component of understanding realistic spectroscopic Hamiltonians that often possess dynamics more closely related to the integrable, near-integrable, and/or mixed phase space regimes. The near-integrable regime is characterized by the introduction of resonances, and the applicability of first order classical perturbation theory. The mixed phase space regime is characterized by the co-existence of near-integrable motion and significant chaotic motion on the same energy surface; i.e. different initial conditions lead to different dynamical behaviors. Explicit expressions are given that can be verified in great detail, at least in some cases. The $`\mathrm{}`$ scalings of the various quantities are deduced as a function of numbers of degrees of freedom, and shown to be different from the chaotic case. In section IV, the intensity-level velocity correlation is computed for single resonance (classically integrable) and multiresonant (classically nonintegrable) two degree-of-freedom Hamiltonians. Section V provides a brief summary and concludes.

## II Intensity-level velocity correlation function : Background

Consider the effective spectroscopic Hamiltonian $`\widehat{H}(𝐚,𝐚^{};\tau )=\widehat{H}_0(𝐧)+\widehat{H}_1(𝐚,𝐚^{};\tau )`$ with $`\tau `$ representing some parameter or parameters of interest. The eigenstates and eigenvalues of $`\widehat{H}`$ will be denoted by $`|\alpha (\tau )`$ and $`E_\alpha (\tau )`$ respectively. In what follows, it is not necessary for this particular choice of the form of the Hamiltonian. Thus, $`\tau `$ could equally well be a parameter of the zeroth-order Hamiltonian. The choice is motivated by a basic interest in determining the localization (or lack thereof) of eigenstates and hence the perturbations which have a large effect in a given energy range. The eigenstates and dynamics associated with $`H_0`$ are assumed to be well understood which is the generic situation in IVR studies. Throughout this article we will focus on vibrational dynamics and ignore the rotational effects. Nevertheless, the basic theory presented below can be applied to the full rovibrational Hamiltonian. Using the Heisenberg correspondence rule,heisen  it is possible to associate a classical Hamiltonian $`H(𝐈,\mathit{\varphi };\tau )=H_0(𝐈)+H_1(𝐈,\mathit{\varphi };\tau )`$ with the quantum $`\widehat{H}`$. The form of the spectroscopic Hamiltonian makes it especially convenient to deal with the classical Hamiltonian in terms of the action-angle variables corresponding to the zeroth-order Hamiltonian. In addition, the classical Hamiltonian is a nonlinear resonant Hamiltonian representing the various resonant perturbations which couple the zeroth-order states leading to the flow of vibrational energy. Depending on $`\tau `$ and the energy of interest, the classical dynamics can exhibit the full dynamical range from integrable to mixed to chaotic behaviors.

Given a special state $`|z`$, the strength functionscar ; stprl ; strength  is defined as

$`S_z(E,\tau )`$ $`=`$ $`{\displaystyle \frac{1}{2\pi \mathrm{}}}{\displaystyle _{\mathrm{}}^{\mathrm{}}}𝑑te^{iEt/\mathrm{}}z|e^{i\widehat{H}(\tau )t/\mathrm{}}|z`$ (1a)
$`=`$ $`{\displaystyle \underset{\alpha }{}}p_{z\alpha }(\tau )\delta (EE_\alpha (\tau ))`$ (1b)
with $`p_{z\alpha }(\tau )=|z|\alpha (\tau )|^2`$ being the overlap intensity. The strength function had been introduced and studied earlier by Hellerstrength  in the context of quantum localization due to eigenstate scarring. The choice of the special state is determined by the system of interest. From a spectroscopic viewpoint, the special state $`|z`$ could be the bright state, and then the strength function is the observed spectrum. Alternatively, one can choose a coherent state corresponding to the phase space image of a certain bright state of interest. In such a case, the intensities are essentially the Husimi function. In Sect. IV, we will primarily choose the latter representation in order to highlight the classical-quantum correspondence of the system.

Beyond scarring, a number of other factors have been found to contribute towards localization effects. For instance, transport barriers like broken separatricesbsep , cantoricantor  or diffusive motiondiffus  in phase space have been linked to localization. One of the hallmarks of localization is the non-democratic response of the system to parametric variation. Specifically the ‘evolution’ of the energy levels of the system, as measured by the level velocities, upon varying a parameter will not be universal. Thus, the independence of eigenvalue and eigenfunction fluctuation measures, a central feature of RMT, is violated. An analysis of the correlation between level velocities $`E_\alpha (\tau )/\tau `$ and the intensities $`p_{z\alpha }(\tau )`$ leads to a better understanding of the deviations from universal behavior and gives insights into the nature of any localization. It is only very recentlystprl  that such a overlap intensity-level velocity correlation has been proposed and shown to be a very sensitive measure. This correlation function is defined as

$$C_z(\tau )=\frac{1}{\sigma _z\sigma _E}p_{z\alpha }(\tau )\frac{E_\alpha (\tau )}{\tau }_E$$
(2)
where $`\sigma _z^2`$ and $`\sigma _E^2`$ are the local variances of the overlap intensities and level velocities, respectively. The brackets denote a local energy average in the neighborhood of $`E`$. As defined, $`C_z(\tau )`$ weights most the states which share common localization characteristics, and measures the tendency of these levels to move in a common direction. Within RMT, it is possible to showcllt  that $`C_z(\tau )=0\pm N^{1/2}`$ with $`N`$ being the effective number of states in the selected energy range. It is important to note that the above result for ergodic systems is true for every choice of $`|z`$. If there is localization, then there is at least one $`|z`$ for which $`C_z(\tau )`$ deviates from zero in a statistically significant way. The usefulness of $`C_z(\tau )`$ has been convincingly demonstrated for the stadium billiardcllt  and the baker’s maplct . A fairly detailed semiclassical theory for the correlation function when the underlying classical dynamics is completely chaotic has been developedcllt . That which is lacking is the theoretical foundation for integrable, near-integrable, and mixed phase space systems.

## III Semiclassical theory for $`C_z(\tau )`$ in the integrable case

The prime motivation of introducing and studying $`C_z(\tau )`$ for the chaotic case has to do with uncovering various localization features of the system and hence deviations from RMT predictions. Evidently, any localization of eigenstates in the chaotic system is subtle and somewhat surprising at first sight. However, localization is the rule rather than the exception for the integrable to mixed phase space regimes. Therefore, it is to be expected to find statistically significant nonzero values for $`C_z(\tau )`$ in such cases.

It is demonstrated ahead that the correlation measure extracts useful information for the non-fully chaotic regimes as well. The utility stems from the fact that a perturbation could non-democratically couple certain states or class of states leading to avoided crossings or like level movements within the particular class. Such a preferential coupling is precisely indicated by $`C_z(\tau )`$ irrespective of the nature of the underlying classical dynamics. In context of the present paper, the effective spectroscopic Hamiltonians typically exhibit a mixed phase space. As mentioned previously, the classical limit of the spectroscopic Hamiltonian is a nonlinear resonant Hamiltonian, and the various nonlinear resonances manifest themselves in different energy ranges. It is quite possible for a molecule in a certain energy range to be dominated by a single Fermi resonance. Single resonant classical Hamiltonians are integrablelicht , and therefore one has conserved quantities, called polyadspoly , associated with the motion. In a different energy range, more than one independent resonance can be important, and classically one has a nonintegrable system. The entire range of behavior from integrable to chaotic is therefore possible. Analyzing a spectrum with $`C_z(\tau )`$ provides one possible route to deciphering the important resonances operative in the energy range of interest. Moreover, as indicated ahead, there are many other insights, such as indications of the effective numbers of degrees of freedom found in the $`\mathrm{}`$-scalings, that one can gain from a study of the correlation function which makes it an attractive candidate for exploring IVR in isolated molecules.

It is important to note that the RMT estimate is only valid for the extreme fully chaotic case. In addition, given the richness of the quantum-classical correspondence for the effective spectroscopic Hamiltonians, it is both necessary and useful to come up with a semiclassical theory for $`C_z(\tau )`$ in such regimes. This section of the paper closely follows the earlier papercllt  concerned with the correlation function for chaotic systems. In the current work an analogus semiclassical theory for the integrable cases is provided. The theory for the near-integrable case will be provided in a later publicationlater .

### III.1 Level Velocities

The purpose of this section is to derive explicit expressions for the mean and variance of the level velocities. From these expressions, the $`\mathrm{}`$-scaling properties can be deduced. The analogous expressions and scalings for the chaotic case have been derived earliercllt . The analysis in this section is important from a classical-quantum correspondence perspective as well as due to the fact that it can be translated into a density of states scaling. To focus on the integrable case we consider a single $`n:m`$ resonant Hamiltonian of the form:

$$H(𝐈,\mathit{\varphi })=H_0(𝐈)+\tau \sqrt{I_1^mI_2^n}\mathrm{cos}(m\varphi _1n\varphi _2)$$
(3)
It is well known that the above Hamiltonian is integrable because of the existence of a conserved quantity $`I=(n/m)I_1+I_2`$ in addition to the energy $`E`$. This constant of the motion $`I`$ is called the polyad number. Since $`H(𝐈,\mathit{\varphi })`$ is integrable one can imagine a canonical transformation $`(𝐈,\mathit{\varphi })(𝐊,𝚽)`$ in terms of which $`H=H(𝐊)`$. Stated differently, the variables $`(𝐊,𝚽)`$ are the action-angle varibales for the single resonance Hamiltonian. Note that the explicit determination of the action-angle variables for an arbitrary single resonance Hamiltonian is very difficult if not impossible. Joyeuxjoy  has given the explicit solutions for resonances with $`m+n4`$ in terms of elliptic functions. However, not being able to construct the explicit transformation does not preclude the existence of the action-angle variables for an integrable system. As pointed out by Joyeux, with a convenient choice of the canonical transformation, it is possible to identify one of the actions $`𝐊`$ with the polyad number $`I`$. Given $`H(𝐊)`$, it is possible to define the frequencies $`\mathbf{}_𝐊H(𝐊)=𝛀(𝐊)`$. The single resonance systems have a slight complication in the sense that the associated phase space has a separatrix. This separatrix, which separates resonant and nonresonant regions in the phase space, cannot be transformed away by a canonical transformation. This is reflected in the fact that different action variables $`𝐊`$ have to be used in the two regions. The separatrix structure will be ignored by assuming that only a local region of the phase space is being investigated in any given case. A more rigorous treatment by taking into account separatrices would involve near-integrable semiclassical theoryamod ; ugt , and that is left for another worklater .

In order to determine an expression for the level velocities in terms of classical quantities and $`\mathrm{}`$, it is convenient to start from the smoothed spectral staircase functioncllt ; keating ; leboeuf :

$$N_ϵ(E,\tau )=\underset{\alpha }{}\theta _ϵ[EE_\alpha (\tau )]$$
(4)
where $`ϵ`$ is an energy smoothing term which will be taken to be smaller than the mean level spacing. Differentiating the staircase function with respect to the parameter $`\tau `$ and taking the energy average yields the identity

$$\frac{N_ϵ(E,\tau )}{\tau }_E=\overline{d}(E,\tau )\frac{E_\alpha (\tau )}{\tau }_\alpha $$
(5)
where $`\overline{d}(E,\tau )`$ is the mean level density. Similarly, assuming a nondegenerate spectrum, it can be shown that

$$\left(\frac{N_ϵ(E,\tau )}{\tau }\right)^2_E=\frac{\overline{d}(E,\tau )}{2\pi ϵ}\left(\frac{E_\alpha (\tau )}{\tau }\right)^2_\alpha $$
(6)
It is possible to write down a semiclassical expression for the spectral staircase function as a sum of an average (Weyl) term and an oscillating term

$$N_ϵ(E,\tau )=\overline{N}(E,\tau )+\stackrel{~}{N}_ϵ(E,\tau )$$
(7)
For an integrable system, the oscillating part according to the theory of Berry and Taborbt  can be written in terms of the rational periodic orbits $`𝐌`$ of $`H(𝐊)`$ as:

$`\stackrel{~}{N}_ϵ(E,\tau )`$ $``$ $`{\displaystyle \frac{2}{\mathrm{}^{(d1)/2}}}{\displaystyle \underset{𝐌}{}}A_𝐌(E,\tau )\mathrm{sin}[\sigma _𝐌]`$ (8)
$`\times \mathrm{exp}\left\{{\displaystyle \frac{ϵT_𝐌(E,\tau )}{\mathrm{}}}\right\}`$
It has been assumed that the curvature of the energy contour is approximately constant locally and in the sum the $`𝐌=0`$ term is excluded. The rational periodic orbits correspond to tori with rotation numbers $`\alpha _{j,k}=\mathrm{\Omega }_j/\mathrm{\Omega }_k=\mu _j/\mu _k`$ with $`\mu _j,\mu _k`$ being coprime integers. $`𝝁`$ specifies the primitive periodic orbit and $`𝐌=r𝝁`$ denotes a specific topology of the closed orbits with $`r`$ being the repetition numberbt . In the above expression for $`\stackrel{~}{N}_ϵ`$, the amplitude and phase factors are given by

$`A_𝐌(E,\tau )`$ $`=`$ $`{\displaystyle \frac{1}{2\pi |𝐌|^{(d+1)/2}|\kappa _𝐌|^{1/2}}}`$ (9a)
$`\sigma _𝐌`$ $`=`$ $`{\displaystyle \frac{S_𝐌(E,\tau )}{\mathrm{}}}{\displaystyle \frac{\pi }{2}}\eta _𝐌+{\displaystyle \frac{\pi }{4}}\beta _𝐌`$ (9b)
where $`\kappa _𝐌`$ is the scalar curvature of the energy contour $`H(𝐊)=E`$. The action corresponding to an orbit of topology $`𝐌`$ is $`S_𝐌=2\pi 𝐊_𝐌𝐌`$, the phase $`\eta _𝐌=𝐌𝜼`$ with $`𝜼`$ being the Maslov indicies and $`\beta _𝐌`$ is equal to the sign of the determinant of the curvature matrix. The period of the corresponding orbit is denoted by $`T_𝐌=rT_𝝁`$.

The oscillatory contribution to the velocity average can be written down and evaluated in the $`\mathrm{}0`$ limit as

$`{\displaystyle \frac{\stackrel{~}{N}_ϵ}{\tau }}_E`$ $`=`$ $`{\displaystyle \frac{2}{\mathrm{}^{(d+1)/2}}}{\displaystyle \underset{𝐌}{}}A_𝐌\left({\displaystyle \frac{S_𝐌}{\tau }}\right)\mathrm{cos}[\sigma _𝐌]`$
$`\times \mathrm{exp}\left\{{\displaystyle \frac{ϵT_𝐌}{\mathrm{}}}\right\}_E`$
$``$ $`{\displaystyle \frac{2}{\mathrm{}^{(d+1)/2}}}{\displaystyle \underset{𝐌}{}}A_𝐌\left({\displaystyle \frac{S_𝐌}{\tau }}\right)`$
$`\times \mathrm{exp}\left\{{\displaystyle \frac{ϵT_𝐌}{\mathrm{}}}\right\}_E\mathrm{cos}[\sigma _𝐌]_E`$
$``$ $`0`$
The above result follows from the argument that for a given orbit the actions and their parametric derivatives are smooth functions of energy. In the semiclassical limit, the derivatives are uncorrelated from the phase term which averages to zero in that limit. Another way to see this is to observe that in performing the energy averaging by stationary phase the dominant contribution comes from orbits satisfying $`\sigma _𝐌^{^{}}(E)=0`$ which correspond to the zero period orbits. By construction, the oscillatory part of the staircase function does not contain the zero-length orbits and hence the average is vanishingly small.

Using the expression for $`\stackrel{~}{N}_ϵ`$ and assuming the different orbits to be uncorrelated from each other in the semiclassical limit, one obtains

$`\left({\displaystyle \frac{E_\alpha (\tau )}{\tau }}\right)^2_E`$ $`=`$ $`{\displaystyle \frac{2\pi ϵ}{\overline{d}}}\left({\displaystyle \frac{\stackrel{~}{N}_ϵ}{\tau }}\right)^2_E`$ (11)
$`=`$ $`{\displaystyle \frac{4\pi ϵ}{\mathrm{}^{(d+1)}\overline{d}}}{\displaystyle \underset{𝐌}{}}A_𝐌^2\left({\displaystyle \frac{S_𝐌}{\tau }}\right)^2`$
$`\times \mathrm{exp}\left\{{\displaystyle \frac{2ϵT_𝐌}{\mathrm{}}}\right\}_E`$
where a diagonal approximation has been used for the sum over rational tori. The off-diagonal terms will contribute to the variance but the dominant contributions and $`\mathrm{}`$-dependence in the semiclassical limit is expected to derive from the diagonal term. For integrable systems, it is reasonable to assumenote  the relation

$$\left(\frac{S_𝐌}{\tau }\right)^2_𝐌\zeta (E,\tau )T^2$$
(12)
The distinction between $`T^2`$ and $`T`$ (relevant to the chaotic case) in the above expression is analogous to the distinction between ballistic and diffusive behaviors, respectively. In analogy to the chaotic case, we invoke the appropriate Hannay-Ozorio sum rulehozsum

$$\underset{𝐌}{}A_𝐌^2\frac{\mathrm{}^d\overline{d}}{2\pi }\frac{dT}{T^2}$$
(13)
to perform the sum over the rational tori. As a result we obtain the dimensionless variance $`\stackrel{~}{\sigma }_E^2`$ as

$$\stackrel{~}{\sigma }_E^2=\overline{d}^2\left(\frac{E_\alpha (\tau )}{\tau }\right)^2_E=\zeta (E,\tau )\overline{d}^2\mathrm{}^{2d}$$
(14)
The relation between the mean square action changes and the mean square level velocities is straightforward involving only the density of states to complete the connection. The $`\mathrm{}`$ dependence drops out easily since the mean level density $`\overline{d}\mathrm{}^d`$ for a $`d`$-degree-of-freedom system. This is to be compared to the scaling $`\stackrel{~}{\sigma }_E^2\mathrm{}^{(d+1)}`$ previously established for chaotic systemscllt . Note that the different $`\mathrm{}`$ scalings are consistent with the notion that chaotic systems’ spectra fluctuate less and are more rigid (constrained) than their integrable systems’ counterparts. Furthermore, both the effective numbers of degrees of freedom and the nature of the dynamics is reflected in the scaling laws. This is a general feature arising over and over. As a consequence of the above result for integrable systems, the variance of the level velocities scales as $`\sigma _E^2O(\mathrm{}^0)`$, and is equal to the variance of the action changes averaged over the appropriate tori. Numerical results in the next section, obtained from application to integrable single resonance Hamiltonians, confirm the derived $`\mathrm{}`$-scaling for $`\stackrel{~}{\sigma }_E^2`$. The full expression has been verified for the rectangular billiard, but only the scalings will be presented in this paper.

### III.2 Overlap intensities

In this section a semiclassical expression for the strength function is derived. The derivation is firmly rooted in the action-angle space and consistent with the Berry-Tabor rational periodic orbit formalism. The $`\mathrm{}`$ scaling of the intensity is derived and shown to be different from that of its chaotic counterpart.

As with the level velocities it is possible to decompose the strength function $`S_z(E,\tau )`$ into an average and an oscillatory part

$$S_z(E,\tau )=\overline{S}_z(E,\tau )+\stackrel{~}{S}_z(E,\tau )$$
(15)
where $`|z`$ is a coherent state and $`p_{z\alpha }=|z|\alpha (\tau )|^2`$. The average or the smooth part is the contribution from zero length trajectories. It can also be viewed as the Fourier transform of the extremely rapid initial decay due to the shortest time scale of the dynamicsstrength .

The average intensities can be written in terms of the smooth part of the strength functions as:

$$p_{z\alpha }(\tau )_\alpha =\frac{1}{\overline{d}}\overline{S}_z(E,\tau )$$
(16)
The quantity of main interest is thus

$$\overline{S}_z(E,\tau )=\frac{1}{(2\pi \mathrm{})^d}A_w(𝐊,𝚽)\delta [EH(𝐊)]𝑑𝐊𝑑𝚽$$
(17)
$`A_w(𝐊,𝚽)`$ is the Wigner transform of a Gaussian wavepacket centered at $`(\overline{𝐊},\overline{𝚽})`$ and can be represented locally in the action angle space $`(𝐊,𝚽)`$ by

$$A_w(𝐊,𝚽)=2^d\mathrm{exp}\left[(\mathrm{\Delta }𝚽)^2\frac{1}{\mathrm{}^2}(\mathrm{\Delta }𝐊)^2\right]$$
(18)
The vectors $`\mathrm{\Delta }𝚽`$ and $`\mathrm{\Delta }𝐊`$ have components $`(\mathrm{\Delta }𝚽)_j=(\mathrm{\Phi }_j\overline{\mathrm{\Phi }}_j)/\sigma _j`$ and $`(\mathrm{\Delta }𝐊)_j=\sigma _j(K_j\overline{K}_j)`$ respectively where $`\sigma _j^2=\mathrm{}/2\overline{K}_j`$. In the above expression, a dimensionless variable has been scaled to one in order to have equal uncertainty scalings in the angle and action variables. As the Hamiltonian is independent of the angles, the angle integrals can be performed in the semiclassical limit. A change of variables $`\mathrm{}𝐳=\mathrm{\Delta }𝐊`$ leads to the expression

$$\overline{S}_z\frac{1}{\pi ^{d/2}}𝑑𝐳e^{𝐳^2}\delta \left[EH\left(\mathrm{}𝐳𝝈^1+\overline{𝐊}\right)\right]$$
(19)
whose evaluation gives:

$`\overline{S}_z`$ $``$ $`{\displaystyle \frac{1}{\pi ^{d/2}}}{\displaystyle 𝑑𝐳e^{𝐳^2}\delta \left[\mathrm{}^{1/2}\underset{j}{}\sqrt{2\overline{K}_j\mathrm{\Omega }_j^2}z_j\right]}`$ (20)
$`=`$ $`\left(2\pi \mathrm{}{\displaystyle \underset{j=1}{\overset{d}{}}}\overline{K}_j\mathrm{\Omega }_j^2\right)^{1/2}`$
The final form results from expanding the Hamiltonian about $`\overline{𝐊}`$ and evaluating the integral at $`E=H(\overline{𝐊})`$, which thus pertains to the peak of the strength function. The $`\mathrm{}`$-scaling can be extracted giving

$$p_{z\alpha }(\tau )\mathrm{}^{d1/2}$$
(21)
It is important that the derived $`\mathrm{}`$-scaling for the intensities is independent of the nature of the dynamics, i.e. integrable or chaotic, as must happen.

The oscillatory part of the strength function is a dynamical object and can be expressed in the action-angle space as

$$\stackrel{~}{S}_z(E,\tau )=\frac{1}{\pi }\mathrm{Im}𝑑𝚽𝑑𝚽^{}z|𝚽G(𝚽,𝚽^{};E)𝚽^{}|z$$
(22)
where $`G(𝚽,𝚽^{};E)`$ is the energy Green’s function. The semiclassical expression for the Green’s function isamod

$`G(𝚽,𝚽^{};E)`$ $``$ $`{\displaystyle \frac{1}{i\mathrm{}(2\pi i\mathrm{})^{(d1)/2}}}{\displaystyle \underset{𝐊}{}}|D_𝐊|^{1/2}`$ (23)
$`\times \mathrm{exp}\left({\displaystyle \frac{i}{\mathrm{}}}S_𝐊(𝚽,𝚽^{};E){\displaystyle \frac{i\pi \nu _𝐊}{2}}\right)`$
where the sum is over all possible trajectories (associated with tori $`𝐊`$) that go from $`𝚽^{}`$ to $`𝚽`$ at an energy $`E`$ and their repetitions. $`S_𝐊(𝚽,𝚽^{};E)`$ is the action associated with a trajectory (including the repetitions) and $`D_𝐊`$ is the usual stability determinant of order $`(2d+1)\times (2d+1)`$ given by

$$D_𝐊=\left|\begin{array}{cc}\frac{^2S_𝐊}{𝚽𝚽^{}}& \frac{^2S_𝐊}{𝚽E}\\ \frac{^2S_𝐊}{E𝚽^{}}& \frac{^2S_𝐊}{E^2}\end{array}\right|$$
(24)
The product of the wavefunctions in the coherent state basis can be obtained via an inverse Wigner transformamod  of the phase space Gaussian. The inverse transform is evaluated by stationary phase to obtain

$`z|𝚽𝚽^{}|z`$ $``$ $`{\displaystyle \frac{1}{\pi ^{d/2}_j\sigma _j}}\mathrm{exp}[{\displaystyle \frac{1}{2}}(\mathrm{\Delta }𝚽)^2{\displaystyle \frac{1}{2}}(\mathrm{\Delta }𝚽^{})^2`$ (25)
$`+`$ $`{\displaystyle \frac{i}{\mathrm{}}}\overline{𝐊}(𝚽𝚽^{})]`$
The evaluation by stationary phase is valid if the location of the Gaussian is away from the edges of the phase space. This is consistent with the fact that we have used a local form of the coherent state in the action-angle coordinates.

The Gaussian localization in action-angle space implies that the dominant contribution to $`\stackrel{~}{S}_z`$ arises from trajectories which are closed on the torus $`𝐊`$ i.e., $`𝚽𝚽^{}=\overline{𝚽}`$. In other words, the dominant contribution comes from rational tori $`𝐊_𝐌`$. This motivates an expansion of the action as

$$S_𝐊(𝚽,𝚽^{};E)S_𝐌(\overline{𝚽},\overline{𝚽};E)+𝐊(𝚽𝚽^{})$$
(26)
In the above expansion the quadratic terms have been neglected. As discussed earlier, the rational torus action $`S_𝐌=2\pi 𝐊_𝐌𝐌`$. This is reasonable for an integrable system since the initial Gaussian in phase space simply shears with time. Using the above expansion of the action, the integrals over the angles can be performed by stationary phase giving

$`\stackrel{~}{S}_z(E,\tau )`$ $``$ $`{\displaystyle \frac{2^d_j\sigma _j}{\mathrm{}(2\pi \mathrm{})^{(d1)/2}}}{\displaystyle \underset{𝐌}{}}|D_𝐌|^{1/2}\mathrm{cos}[\sigma _𝐌]`$ (27)
$`\times e^{(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}`$
The above result for the oscillatory part of the strength function can be used to obtain the variance of intensities as

$`\sigma _z^2`$ $`=`$ $`{\displaystyle \frac{2\pi ϵ}{\overline{d}}}\stackrel{~}{S}_z^2(E,\tau )_E`$ (28b)
$`=`$ $`{\displaystyle \frac{ϵ2^{2d1}_j\sigma _j^2}{\overline{d}(2\pi )^{d2}\mathrm{}^{d+1}}}{\displaystyle \underset{𝐌}{}}|D_𝐌|e^{2(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}`$
$`\times e^{2ϵT_𝐌/\mathrm{}}_E`$
where we have used the diagonal approximation for the sum over $`𝐌`$. Since the trace of the Green function is the density of states given by Berry and Taborbt  and the density of states is the energy derivative of the spectral staircase function, then $`|D_𝐌|=T_𝐌^2A_𝐌^2/(2\pi )^{d1}`$. Hence, given the Hannay-Ozorio sum rulehozsum  for $`_𝐌A_𝐌^2`$ stated in the previous section, here

$$\underset{𝐌}{}|D_𝐌|\frac{\mathrm{}^d\overline{d}}{(2\pi )^d}𝑑T$$
(29)
It follows that

$$\sigma _z^2\frac{_j\sigma _j^2}{\pi ^{2d2}}e^{2(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}_𝐌$$
(30)
which again has been verified for the rectangular billiard, but will not be shown here. The leading order $`\mathrm{}`$-scaling of the intensity variance is

$$\sigma _z^2\mathrm{}^d$$
(31)
In the chaotic caseerror , the RMT expectation is $`\sigma _z^2\mathrm{}^{2d1}`$ which follows from the scaling of $`p_{z\alpha }`$. The intensities follow a Porter-Thomas distribution, which has only one parameter given by its mean; the variance is always twice the square of the mean. Again, the integrable limit scaling of the variance of the intensities is different from the chaotic limit which is a manifestation of the differing nature of the underlying classical dynamics. It follows that because the variance is on a much greater scale, the distribution of strengths is necessarily singular for the integrable case in the limit of $`\mathrm{}0`$ (i.e. mostly near zero values except for a few extremely large values).

### III.3 Correlation function

The semiclassical theory for overlap intensities and level velocities outlined in the previous subsections can now be used to construct the correlation function. Beginning with the covariance, it can be shown that

$`Cov_z(\tau )`$ $`=`$ $`p_{z\alpha }(\tau ){\displaystyle \frac{E_\alpha (\tau )}{\tau }}_\alpha `$ (32)
$`=`$ $`{\displaystyle \frac{2\pi ϵ}{\overline{d}}}S_z(E,\tau ){\displaystyle \frac{N(E,\tau )}{\tau }}_E`$
The semiclassical expressions for the strength function and the parametric derivative of the staircase function give

$`Cov_z(\tau )`$ $`=`$ $`{\displaystyle \frac{ϵ2^d_j\sigma _j}{\overline{d}\mathrm{}^{d+1}(2\pi )^{(d3)/2}}}{\displaystyle \underset{𝐌}{}}|A_𝐌||D_𝐌|^{1/2}\left({\displaystyle \frac{S_𝐌}{\tau }}\right)`$ (33)
$`\times e^{(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}e^{2ϵT_𝐌/\mathrm{}}_E`$
Again, the diagonal approximation has been made in the above expression. Following arguments parallel to those in the previous section leads to the expression

$`Cov_z(\tau )`$ $`=`$ $`{\displaystyle \frac{2^d_j\sigma _j}{(2\pi )^{d1}\tau _H}}{\displaystyle }dT{\displaystyle \frac{1}{T}}e^{2T/\tau _H}\left({\displaystyle \frac{S_𝐌}{\tau }}\right)`$ (34)
$`\times e^{(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}_𝐌`$
where $`\tau _H=\mathrm{}/ϵ`$ is the Heisenberg time. In order to make further progress in understanding the correlation function, it is necessary to know the time dependence of the $`𝐌`$-averaged expression. It is important to note that the Gaussian weighting factor will not decouple from the paramteric action derivative at long times. Assuming that the parametric derivative $`𝐊_𝐌/\tau `$ to be a weak function of the period gives the approximation

$$\left(\frac{S_𝐌}{\tau }\right)e^{(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}_𝐌T\xi (\tau )$$
(35)
leading to the final result

$$Cov_z(\tau )\frac{\xi (\tau )_j\sigma _j}{\pi ^{d1}}$$
(36)
Combining this with the results of the previous subsections generates the semiclassical expression for the correlation function. It is

$$C_z(\tau )\frac{\xi (\tau )}{\zeta ^{1/2}(E,\tau )e^{2(\mathrm{\Delta }𝐊_𝐌)^2/\mathrm{}^2}_𝐌^{1/2}}$$
(37)
Interestingly, there is classical information represented in the correlation function that is not in the covariance; therefore considering the separate “components” of the correlation function (or considering both the covariance and correlation functions) gives the greatest information about the system. In the semiclassical limit, the above result implies that $`Cov_z(\tau )\mathrm{}^{d/2}`$ for integrable systems whereas the correlation $`C_z(\tau )\mathrm{}^0`$ to leading order. This last result had to emerge from the semiclassical calculations. Otherwise strong localization could not persist in integrable systems in the limit as $`\mathrm{}0`$, and multidimensional WKB theory could not work.

## IV Application to a model effective Hamiltonian

In order to illustrate the usefulness of the intensity-level velocity correlation measure introduced in the previous sections, consider a simple two dimensional effective Hamiltonian

$$\widehat{H}(𝐧,𝐚,𝐚^{})=\widehat{H}_0(𝐧)+\tau _{11}\widehat{H}_{1:1}(𝐚,𝐚^{})+\tau _{21}\widehat{H}_{2:1}(𝐚,𝐚^{})$$
(38)
where $`\widehat{H}_0(𝐧)`$ is the zeroth-order, anharmonic, vibrational Hamiltonian given by

$$\widehat{H}_0(𝐧)=\omega _1N_1+\omega _2N_2+x_{11}N_1^2+x_{22}N_2^2$$
(39)
The zeroth-order frequencies of the two modes are denoted by $`\omega _1,\omega _2`$. The mode occupation numbers are $`N_j(n_j+1/2)`$ and the mode anharmonicities are denoted by $`x_{jj}`$. The full Hamiltonian is multiresonant in that the zeroth-order anharmonic modes are coupled by a $`1:1`$ and a $`2:1`$ resonant perturbation defined in terms of the operators $`𝐚,𝐚^{}`$ as

$`\widehat{H}_{1:1}(𝐚,𝐚^{})`$ $`=`$ $`a_1^{}a_2+a_2^{}a_1`$
$`\widehat{H}_{2:1}(𝐚,𝐚^{})`$ $`=`$ $`a_1^{}a_2a_2+a_2^{}a_2^{}a_1`$ (40)
The parameters $`\tau _{11}`$ and $`\tau _{21}`$ measure the strength of the corresponding resonant perturbations. The above spectroscopic Hamiltonian $`\widehat{H}`$ arises in many instances in molecular spectroscopy. For example, with $`\tau _{21}=0`$ and for identical oscillators, the effective Hamiltonian modelswater1  the stretching modes of H2O. On the other hand with $`\tau _{11}=0`$, the effective Hamiltonian models the Fermi resonant interactions between the stretch and the bend modes in HCX3 moleculesqu1 . We have chosen a multiresonant Hamiltonian to model systems where two zeroth-order modes of interest can get coupled by one or both of the resonances depending on the pertinent energy range. The parameter values chosen for this work are $`\omega _1=1.0,\omega _2=0.8,x_{11}=0.04`$, and $`x_{22}=0.02`$.

The classical limit Hamiltonian corresponding to the quantum $`\widehat{H}`$ can be easily constructed using the Heisenberg correspondence ruleheisen  and shown to be the following nonlinear, multiresonant Hamiltonian:

$`H(𝐈,\mathit{\varphi })`$ $`=`$ $`\omega _1I_1+\omega _2I_2+x_{11}I_1^2+x_{22}I_2^2`$ (41)
$`+`$ $`2\tau _{11}(I_1I_2)^{1/2}\mathrm{cos}(\varphi _1\varphi _2)`$
$`+`$ $`2\tau _{21}(I_1I_2^2)^{1/2}\mathrm{cos}(\varphi _12\varphi _2)`$
It is well known that with either $`\tau _{11}`$ or $`\tau _{21}`$ equal to zero the classical Hamiltonian is still integrable whereas with both the coupling strengths nonzero, the system is nonintegrable. For the choice of the parameter values made above and noting that the model Hamiltonian is two dimensional, the density of states is expectedly small. In order to simulate a high density of states situation we will make use of the following scalingqs5  to reduce the effective value of $`\mathrm{}\mathrm{}/c`$:

$`\omega _j`$ $``$ $`\overline{\omega }_j=\omega _j/c,x_{ij}\overline{x}_{ij}=x_{ij}/c^2,`$
$`\tau _{11}`$ $``$ $`\overline{\tau }_{11}=\tau _{11}/c,\tau _{21}\overline{\tau }_{21}=\tau _{21}/c^{3/2}`$ (42)
Note that for most of the results presented in this work we have used $`\mathrm{}=1`$. Elsewhere, the scaling will be explicitly given.

In computing the correlation functions shown below, the level velocities have been constrained to be zero-centeredcllt . This is achieved by subtracting out the mean level velocity, in the energy range of interest, from the individual level velocities; this results in no loss of generality. Also, the energy window is chosen such that the classical dynamics are essentially the same throughout the range. This is essential since any bifurcation in the system will alterparisri  the level velocity structure. The problem of qualitative changes in the correlations due to the various bifurcations will not be addressed here. The “bright state” $`|z`$ is chosen to be a coherent state centered on $`(J,\psi )`$ with $`J=(I_1I_2)/2`$ and $`\psi =(\varphi _1\varphi _2)`$. This choice of $`|z`$ is convenient for studying the system’s classical-quantum correspondence via comparisons to the appropriate classical Poincaré surface of sections. The details for the construction of the surface of sections and determining the intensities $`p_{z\alpha }`$ can be found in an earlier workwater1 . The level velocities are computed by invoking the Hellman-Feynman theorem and given by

$$\frac{E_\alpha }{\tau _j}=\alpha |\widehat{V}_j|\alpha $$
(43)
Note the important point that the level velocities themselves are basis independent objects. The energy range used for computing the correlation is fixed to be $`[8,9]`$. For this choice of the energy range, the eigenvalues and eigenstates are well converged in the zeroth-order number basis. The choice of the energy range is also motivated by the fact that the two resonances overlap without leading to large scale stochasticity in the classical phase space.

### IV.1 Example of integrable cases

The multiresonant Hamiltonian has two integrable, single resonance subsystems that can be obtained by setting $`\tau _{11}0,\tau _{21}=0`$ and $`\tau _{11}=0,\tau _{21}0`$. In the former case one obtains a $`1:1`$ system and in the latter case a $`2:1`$ system is obtained. Studying these integrable subsystems serves two main purposes. First, the evaluation of the correlation function $`C_z(\tau )`$ helps provide a baseline for the later interpretations in the nonintegrable regime. Secondly, the $`\mathrm{}`$-scalings predicted for $`\sigma _\alpha `$ and $`\sigma _E`$ can be verified. In principle, the full semiclassical expressions could be verified. However, that would require the calculation of a large set of periodic orbits which would be time consuming for this system; the expressions have been verified for the simpler system of a rectangular billiard. Note that at the outset it is expected that the correlation will be significant for many choices of the coherent states $`|z`$. Our concern, however, is to determine the nature of $`C_z(\tau )`$ for the integrable systems and compare it to the classical phase space structures.

Throughout this section the nonzero coupling strength is set equal to 10-2. In Fig. (1), we show the classical $`(J,\psi )`$ surface of section at an energy $`E=8.5`$ for the integrable $`1:1`$ and the $`2:1`$ cases, respectively. The appropriate resonant and nonresonant regions for the two cases can be clearly identified. In the energy range of interest, there are no bifurcations in the classical phase space. In Fig. (2), we show the intensity and dimensionless level velocity variances as a function of $`\mathrm{}`$ and $`\mathrm{}^2`$, respectively (so that the points lie on a straight line), for the two subsystems. In the $`1:1`$ case, the coherent state is located at $`|z_A=(0,1)`$ in the $`(J,\psi )`$ surface of section whereas in the $`2:1`$ case, the coherent state is located at $`|z_B=(0.5,3.75)`$. The particular choices of the coherent states are made such that they are located inside the resonance zones and close to the appropriate stable periodic orbits. The agreement with the theoretical predictions is fairly good and other choices of $`|z`$ yield similar results except near the edges of the $`(J,\psi )`$ plane. Although not shown here, the scaling of the average intensities $`p_{z\alpha }`$ is also consistent with the theoretical values derived in the previous section.

We now turn our attention to the intensity-level velocity correlations and compute them as a function of the coherent states spanning the surface of section; each correlation result is plotted at the phase space center of the coherent state being used, and which thereby gives a full phase space portrait of the correlation function’s behavior. In Fig. (3), we show the positive and negative parts of the correlation $`C_z(\tau _{11})`$, respectively. The prime reason for showing the positive and negative contributions of $`C_z(\tau _{11})`$ separately is that this directly reflects the phase space localization features of states with positive and negative level velocities. As mentioned in the introduction, the relative sign of the level velocities in integrable and mixed systems is intimately connected to the localization of the states about stable and unstable structures in the phase space. For $`\mathrm{}=1`$, the number of states in the energy range is $`27`$ for both the $`1:1`$ and the $`2:1`$ systems. Despite the low density of states, Fig. (3a) shows large positive, statistically significant values for $`C_z(\tau _{11})`$ around the stable periodic orbits. Similarly from Fig. (3b), notice the large values for the negative correlation around the unstable periodic orbit; the positive and negative peak values are $`0.92`$ and $`0.42`$ respectively. The results for the integrable $`2:1`$ case are shown in Fig. (4). Once again the correlation $`C_z(\tau _{21})`$ takes on large positive ($`0.83`$) and negative ($`0.65`$) values at the stable and unstable periodic orbits respectively. The strong positive peaks in the correlations are reminiscent of similar structures arising due to the bouncing ball states in the stadium systemcllt . Although the stadium is completely chaotic, the analogy to the present integrable case is appropriate. This has to do with the fact that a previous workfinger  has shown that the states localized in the center of the resonance zone exhibit linear parametric motion. It is well knowntakhas  that the bouncing ball states also exhibit linear parametric motion and, indeed, a WKB quantization of such states leads tocllt  $`\stackrel{~}{\sigma }_E\mathrm{}^2`$ which compares favorably with our integrable system theory. Strong correlations at the classical fixed points have been observed earlierlct  in the context of the bakers and the standard map. The present results are consistent with the previous work, and a significant observation is that the correlation is a faithful representation of the relevant resonant portion of the phase space. In other words, depending on the parameter being varied, the corresponding region of the classical phase space is highlighted. A particularly interesting feature of the correlations in Figs. (3,4) has to do with a noticeable dip at the classical fixed points. This seems to be a fairly general feature associated with fixed points in the classical phase space. In a sense, the correlation, constructed with quantum eigenvalues and eigenstates, is capable of locating the periodic orbits of the system. We do not intend to give a detailed account of this feature except to mention that it arises from the large intensity variance $`\sigma _\alpha `$ at the fixed points.

### IV.2 Example of mixed phase space case

Consider the full multiresonant Hamiltonian with $`\tau _{11}=\tau _{21}=10^2`$. The theory developed in this work is not strictly applicable in this regime, although if prior experience can be used as a guide, it will be relevant to the regular phase space regions or KAM islands (as will be seen ahead). On the other hand, a mixed phase space is generic to many systems, and it is essential to understand the structure of the correlation function in such cases. It is important to note that a theoretical basis for the mixed phase space case is exceedingly difficult, and currently the next best approach is to attemptlater  a description for the near-integrable systems.

Four surfaces of section in the energy range $`[8,9]`$ are shown in Fig. (5). The classical dynamics does not vary significantly in this energy range and exhibits a mixed phase space. The two resonances have overlapped, generating stochastic regions in the phase space. Yet, it is still possible to identify the stable fixed points corresponding to the two resonances. Figure (6) shows the positive and negative components of the correlation function $`C_z(\tau _{11})`$. As compared to the integrable case in Fig. (3), there are many common features including the large positive values at the stable fixed point and the associated dip. This indicates that the linear parametric motion persists at these energies and coupling strengths. There are, however, important differences between the mixed phase space and the integrable cases. In particular the negative regions of the correlation in Fig. (6b) show a lot more structure. The dip associated with the unstable fixed point is hardly noticeable. This is consistent with the destruction of the separatrix due to the overlap of the two primary resonances. Notice that the negative values of the correlation are mainly associated with the chaotic regions of the phase space as opposed to the positive values shown in Fig. (6a). The nonuniformity of the negative $`C_z(\tau _{11})`$ implies that there exist eigenstates in the energy range which are affected strongly by the $`1:1`$ perturbation and which share common localization features. Figure (6a) clearly indicates the existence of strongly localized states close to the center of the $`1:1`$ resonance channel. Roughly speaking, although in the limit of strongly chaotic dynamics, the chaotic region should show no structure, the chaotic region in a mixed phase space system has a great deal of structure related to cantori or broken separatrices, and “stickiness” whereby trajectories become trapped near tiny regular regions. Transport is not rapid and uniform, and the localizing effects on the eigenstates show up in the correlation function. In order for more details of this structure to be visible in Fig. (6a), a much higher density of states (smaller value of $`\mathrm{}`$) would have to be used.

Figure (7) shows the analogus results for the correlation $`C_z(\tau _{21})`$. The results are similar to that of the $`1:1`$ case. Parametric variations in $`\tau _{21}`$ highlight the $`2:1`$ region of the phase space. Note that it is quite possible to choose a state $`|z`$ such that both the correlations are negligibly small. This implies that the chosen $`|z`$ is not strongly affected by either of the resonances. Thus, if a coherent state $`|z`$ lies in a region that is strongly affected by a certain perturbation, then the associated correlation will highlight the relevant part of the phase space.

The model system considered in this paper has two degrees of freedom. Consequently it is possible to obtain detailed information about the phase space structure and localization features of eigenstates. In three or more degrees of freedom systems the standard approach of surface of sections and phase space distribution functions cannot be employed for well known reasonslicht . The results in this section demonstrate that the correlation function highlights the various classical structures (periodic orbits, tori, etc.) in the phase space. Nevertheless, the correlation function is not subject to the usual constraints that have to be satisfied by a surface of section. This suggests that it is possible to compute the correlation over various reduced dimensionality spaces and gain insights into the system. For instance, the correlation could be averaged over the angle variables, and obtain an average correlation as a function of the actions alone. As a simple example in Fig. (8), we show the angle averaged correlations $`C_z(\tau )_𝜽`$ corresponding to the results in Fig. (6,7). The peaks of the averaged correlation function are very close to the center of the respective resonance zones. Hence, $`C_z(\tau )_𝜽`$ is providing information on the local resonance structure associated with a particular $`|z`$ which is linkedrev  experimentally to the gateway states.

As metioned in the introduction, experimentally there is access to very few bright states in a particular energy range. One of the important questions, given the bright state and its associated spectrum, concerns the relative effect of the various perturbations in a certain energy range. It is of particular interest to demonstrate how the above question can be addressed with the overlap intensity-level velocity correlation function. In order to determine the usefulness of the correlation in this regard, we select three different bright states $`|z_A,|z_B`$ and, $`|z_C`$. The first two have been introduced in the previous subsection, and the third one $`|z_C`$ is centered at $`(J,\psi )=(0.6,1.5)`$ corresponding to the chaotic region of the phase space. The spectra associated with the three states are shown in Fig. (9). In order to have a higher density of states, the value of $`\mathrm{}=1/3`$. For the chosen value of $`\mathrm{}`$, there are $`250`$ states in the energy range shown in Fig. (9). The correlations $`C_z(\tau _{11})`$ and $`C_z(\tau _{21})`$ associated with each of the spectra are also shown. It is clear that for the bright state $`|z_A`$ the $`1:1`$ perturbation has a much larger effect as compared to the $`2:1`$ perturbation. The roles are reversed in the case of the bright state $`|z_B`$. In the case of the state $`|z_C`$, both of the correlations are negative and small. However, the correlations are not insignificant since, as a rough estimate, a RMT-like result would give $`C_z0\pm 0.063`$. Moreover, the correlation is almost two times larger for the $`1:1`$ perturbation as compared to the $`2:1`$ perturbation. ¿From a time-dependent point of view, recurrences in the survival amplitude $`z|z(t)`$ are connected to classical structures in the phase space. The correlation function is providing clues as to the precise nature of the classical phase space structures which are dictating the dynamics of the bright state of interest.

Finally, a closer look at the correlations shown in Figs. (6, 7), compared to their integrable counterparts, indicates the spreading of the correlation due to the destruction of barriers in the phase space. The classical surfaces of sections shown in Fig. (5) have been computed up to times significantly larger than the heisenberg time $`\tau _H`$. The fact that the correlations are indicating “amplitude transport” through broken KAM tori or separatrices gives a unique probe of the transport. Moreover, the uneven spreading of the correlations suggests the existence of partial barriers. This observation raises the possibility of understanding transport phenomena in the phase space via the correlation function. Further work is warranted to establish what information is contained, and how to extract it from the correlation behaviors in the chaotic regions of mixed phase space systems.

## V Summary and Conclusions

In this paper we have explored the possibility of studying IVR through the overlap intensity-level velocity correlator. A semiclassical theory for the correlator has been developed in the case that the underlying classical dynamics is integrable. Combined with the earlier workcllt  providing the semiclassical theory for chaotic systems, the correlator is an ideal candidate for a detailed study of the classical-quantum correspondence for a general system. Application to an effective spectroscopic Hamiltonian clearly supports our point of view. Although the model Hamiltonian used in the present study is two dimensional, it is evident that the correlator is well suited for multidimensional systems with a high density of states. It was demonstrated that choosing different parameters, corresponding to the different perturbations, highlighted the appropriate parts of the phase space displaying prominent localization features. The fact that these localization features are often connected to classical structures like tori, resonance zones, and periodic orbits provides an avenue to understand the relative importance of the various perturbations in a given energy range. From the IVR perspective this information is intimately connected to the dynamics of an initial bright state of interest. If the dynamics of a particular bright state is influenced strongly by specific classical structures, then the correlation will invariably reveal the relevant terms in the molecular Hamiltonian which play an important role.

The manner in which we have applied the technique in this work is useful in situations where one has an effective spectroscopic Hamiltonian at hand. For a specific molecule, the coupling strengths are fixed and experimentally one cannot vary the perturbation strengths in a direct fashion. However, the standard practice of isotopic labeling/substitution achieves this in an indirect, albeit uncontrollable, way since such studiesdark  do vary the nature of the dark states relative to the bright state. A more direct possibility would be to use various external fields or parameters to generate the level motions; but then the connection between the fields and the possible Hamiltonian terms would need to be explored. From a theoretical standpoint, the computation of the intensities requires the eigenstates which can be a daunting task for molecules with a large number of coupled modes. Significant advances in computational methods in recent years is certainly encouragingrev5 . However, under some circumstances, a hybrid approach of correlating the experimental intensities with the computed level velocities could be tried. Another possibility is to adapt the MFD approachmfd2  where intensities are related to the parametric derivatives of the eigenvalues.

Throughout this paper we have assumed the availability of an eigenstate resolved spectrum for the system. At a coarser level, corresponding to shorter time scales, there is the dispersed fluorescence spectrum which contains key information regarding IVR and approximately conserved quantities. It would be interesting to have an explicit time-dependent view of the IVR process i.e., deciding the perturbations which dictate the dynamics of a bright state over different time scales. For this purpose, it is appropriate to work with the finite time or smoothed strength functionstrength  defined as:

$$S_z^{(T)}(E,\tau )=\frac{1}{2\pi \mathrm{}}_T^T𝑑te^{iEt/\mathrm{}}z|e^{i\widehat{H}(\tau )t/\mathrm{}}|z$$
(44)
There is a problem with using the finite time strength function since the concept of eigenstates and hence that of level velocities is not meaningful. We are currently exploring the correct finite time analog of the correlator.

As stated earlier there are many aspects of the intensity-level velocity correlator which warrant further studies. Foremost among them are phase space transport, spectroscopy in external fields and quantum versus classical routes to localization. Efforts are currently underway to systematically approach and understand these features in molecular systems.

## VI Acknowledgments

This work was supported by grants from the National Science Foundation, PHY-0098027, and the Office of Naval Research, N00014-98-1-0079. SK thanks Tapas Chakraborty for helpful discussions and the Department of Science and Technology and, Council for Scientific and Industrial Research, India for financial support.