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Ann. Rev. Phys. Chem. 1985. 36:277320 Copyright © 1985 by Annual Reviews Inc. All rights reserved
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MOLECULAR DYNAMICS BEYOND THE ADIABATIC APPROXIMATION: .New Experiments and Theory
Robert L. Whetten, Edward R. Grant Gre~7ory S. Ezra, and
Department of Chemistry, Baker Laboratory, Cornell University, Ithaca, New York 14853 INTRODUCTION At the heart of the quantummechanical description of molecular structure and dynamics lies the adiabatic or BornOppenheimerapproximation (1, 2). Starting with an assumptionof separability of time scales for nuclear and electronic motion, a familiar picture emerges of nuclei subject to welldefined forces correspondingto the potential energy surface for a particular electronic state. Althoughthe wellestablished success of these ideas in the areas of molecular spectroscopy (35) and reaction dynamics(69) is likely to secure the adiabatic approximation as a continuing foundation of molecular science, the range of dynamical processes that lies within its scope is far from complete. Recent experimental and theoretical advances in particular are beginning to yield a coherent understanding of several phenomena that, far from requiring minor corrections to the adiabatic approximation for their explanation, by their very nature exist entirely outside its framework. Examples of importance in diverse areas of chemistry and physics range from the dynamicsof radiationless decay (1015) and nonadiabatic processes in chemical reactions (1619) to spectroscopy of excited (2023) and ionized (2426) states of isolated molecules,from single collision electronic energy transfer (2741) to exeiton (42) and soliton (43) dynamicsand spinlattice relaxation (44). Specialized reviews on these topics are available. 277 0066426X/85/11010277502.00
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In this article we adopt a much narrower view, concentrating on nonadiabatic bound states. Considerable recent progress has been made in this area, with a strong and very profitable interaction betweentheory and experiment. By emphasizing some theoretically tractable models that though simple are capable of quantitatively interpreting stateoftheart spectroscopic measurements,we hope to provide the basis for an appreciation of the role of nonadiabatic coupling in the wider contexts noted above. Weendeavor in particular to use the treatment of nonadiabatic states to illuminate the nature of the simpler or less rich dynamics obtained in the limit that the adiabatic approximationis valid. In the past few years a numberof monographsand review articles have been devoted to subjects closely related to the material discussed here. Among these, special attention is drawnto the following : 1. First is the recent text of Bersuker(19). Aside from being a soundreview of the principles of molecular dynamics, this work is also extremely important because it extends beyond the formal chemical physicist’s viewpoint of eigenstates and energy level patterns and makes contact with qualitative molecular orbital theories that are of widespreaduse in organic and inorganic chemistry. It is accompanied by an exhaustive bibliography of work up to 1979 (45). 2. The recent reviews by K6ppelet al (46, 47) drawspecial attention to the novel effects encountered when more than one vibrational, mode interacts with electronic states. Fromthis starting point K6ppelet al have been led to apply the statistical theory of energy level spacings to characterize complexvibrational manifolds, and to identify important applications in the field of irreversible radiationless decay. 3. Judd (48) and Carrington (49) have reviewed the qualitative form adiabatic potential surfaces in the vicinity of intersections. (See also 5056.) This work generally uses group theory to deduce the form of the surface, but leaves off at the point at which an explicit connection with nonadiabatic dynamics must be made. 4. Nonadiabaticprocesses in the solid state are covered in the classic work of Davydov (42) (see also 43), in Englman’s comprehensive text (44), in Bersuker & Polinger’s review of cooperative effects and phase transitions (57). Reviewsin more peripheral areas are cited below. Our review of nonadiabatic bound states begins with a discussion of a quantumformalism first developed over 25 years ago. This formalism has recently been remarkably successful in providing a complete quantitative analysis of a molecular vibronic spectrum, as discussed below. However, the intractability of the quantum approach for treating larger systems remains an outstanding problem. Experimental manifestations of bound
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state nonadiabaticity are reviewed next, with an emphasis on isolated molecules. Twoexceptionally promising developments are highlighted, both relating to Rydbergstates. Finally, several semiclassical theories of nonadiabatic processes are briefly reviewed, and vibronic dynamicsin the vicinity of a conical intersection are explored within the frameworkof the classical electron model. QUANTUM THEORY OF MOLECULAR STATES NONADIABATIC
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The quantum theory of molecular bound states beyond the adiabatic approximation has until recently remained well ahead of experiment in the investigation of spectroscopic and dynamical consequences of nonadiabaticity. This situation is now rapidly changing, as shown by advances described in the next section. In view of the nature of the experimentalwork discussed there, attention is restricted here to effects that occur in isolated polyatomic molecules; this leaves ample scope for treatment of an interesting range of new and unexpected phenomena. A longstanding difficulty in the theory has been the lack of a simple meansfor visualizing the effects of nonadiabaticity. This has been partially remedied by several recent calculations (5861a) of nuclear probability densities corresponding to exact vibronic states; comparison of these densities with those derived from purely adiabatic functions, as discussed belowfor triazine ; and by the development classical analog hamiltonians of for studying nonadiabatic dynamics in multimode systems. The discussion to follow is a brief account of theoretical work directed toward (a) understanding the implications of electronic degeneracy and the consequentstructural instabilities in molecules such as X3(X = Li, Cu, Na, Ag, K) or planar C5H5 C6H ; (b) the nature of vibronic states in the and ~vicinity of degeneracies, and the most useful representations for describing electronic state evolution; (c) problems of localization due to effects higherorder couplings; (d) interpretation of complex spectra in nonadiabatic systems and extraction of nonadiabaticity parameters from experiment; and (e) extension to multimode problems and related phenomenasuch as radiationless electronic decay. Reviews of the theory of molecular bound states beyond the adiabatic approximation have been given by LonguetHiggins (62), Kolos (63), ~)zkan & Goodman(64), Bishop & Cheung (65), and Lathouwers Leuven (66). Various aspects of fully quantum mechanical approaches nonadiabatic transitions in molecular collisions have been reviewed by Baer (38, 40), Garrett &Truhlar (35), Rebentrost (36), Tully (17), Child 32), Macias & Riera (41), and Kleyn, Los & Gislason (39). Several
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280 WHETTEN, EZRA & GRANT
definitions of the term "vibronic coupling" have been discussed in the useful article by Azumi& Matsuzaki (67). General Formalism
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Most of the important manifestations of nonadiabaticity are present in the simplest case of a symmetrybased electronic degeneracy; hence we consider this class of problemin somedetail [the results are extendable to treat less symmetricalcases (68)]. In the absence of electronic degeneracy, a good approximation to the molecular wavefunction is the familiar BornOppenheimeror adiabatic product of electronic and nuclear functions. In the vicinity of an nfold degeneracy, known to be ubiquitous in the space spanned by polyatomic vibrational coordinates (54, 6972), it is therefore natural to invoke expansion in somendimensional electronic basis. These general considerations can be formalized as follows: The timeindependent spinfree Schr6dinger equation for an isolated molecule is written : [TN+ H,(Q)]tI’,(q, Q) =E,~P.(q,
where TN is the nuclear kinetic energy operator,
1.
and H~(Q) is the remainder
of the full molecular hamiltonian: H~(Q)= T~ + U~ + U~ + U~. 2.
Note that this electronic hamiltonian, depends He(Q), parametrically on the nuclear coordinates, denoted collectivelyQ. Terms Eq.2 arcthe by in electronic kinetic energy, intcrelectronic the repulsion potential, electronnuclear attraction,internuclear and repulsion, respectively. Separation into coupled vibrational equations bc cffcctcd can using either twodistinct of strategies : Oneinvolves useof diabatic the states (62,73).Theexact molecular wavcfunction is expanded follows as : u,,.(q, Q) =~, ~’k(q ; Qo)zk(Q), 3.
where the orthonormal electronic states ~’k arc defined by solving the electronic Schr6dingcr equation at a chosen reference configuration Q0 : He(Qo)~’,(q) = E°~ d/~(q).
The vibrational wavcfunctions Zk arc determined by a set of coupled equations with hamiltonian matrix elements Hk.k" T~bk.k"<~kIHe(Q)l~k’>. = + 5.
Annual Reviews www.annualreviews.org/aronline NONADIABATIC DYNAMICS 281 Note that the nuclear kinetic energy is diagonal in the diabatic basis, and the matrix elements of He(Q)can be further expandedto give: 6. Hk, = (T~v+ E~+AUmv k, ) ~k~, + (~,~IA Ue~v[~%,). Each diagonal element therefore defines an effective vibrational hamiltonian, consisting of the nuclear kinetic energy operator plus the HellmannFeynman (74, 75) potential for nuclear motion given by the internuclear repulsions and the attraction to the electronic charge distribution [~ff~k]. These vibrational hamiltonians neglect, however, all response of the electronic state to changing nuclear configuration. The neglected offdiagonal coupling terms derive from the AU~s term, and it is therefore the change in the electronnuclear attractive potential with nuclear configuration that induces mixing of diabati¢ basis states, ~ving rise to both adiabatic and nonadiabatic correlation of electronic and nuclear motion. Wenote that greatly improvedfo~s of diabatic bases for practical solution of Eq. 1 are possible (46, 47, 7~78). An alternative strategy is to expandW(q, Q) using a basis of adiabatic electronic states: V,(q, Q) = E ~m(q; Q)Zm(Q), where the ~,(q; Q) are solutions of the electronic Schr6dinger equation He(Q)~m(q Q) = Em(Q)Om(q ; 8. 7.
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and depend parametrically on the nuclear coordinates {Q}. Expansion 7 is the BornHuang series (2), and the electronic eigenvalues E~(~) define usual adiabatic potential surNces. A set of coupled equations can be obtained for the adiabatic vibrational amplitudes, ~, wherethe coupling is nowinduced by offdiagonal matrix elements of the nuclear kinetic energy (61a,b). Diabatic states are in many ways more convenient for practical calculations, because they correspond to fixed electronic configurations, whereasadiabatic electronic states and associated potential energy surNces emerge naturally from quantum che~stry computations (41). TwoSla~e Syslems The simplest case of a symmetryinducedtwofold electronic degeneracy (n = 2) interacting with a sinNe doublydegenerate vibrational mode,such as the trigonalmolecule E x ~ problem, is important in the interpretation of sNctra discussed in the next section, and, additionally, it ~ustrates several general and unusual consequen~s of nonadiabaticity. To first order, the corresponding adiabatic surNces show a linear divergence from the
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WHETTEN, EZRA & GRANT
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degeneracypoint, characteristic of a conical intersection (69); addition of harmonic restoring force leads to the familiar cylindrically symmetric sombrero picture shown in Figure 1. Addition of higherorder coupling terms breaks the cylindrical symmetryby putting threefold symmetric ripples in the surfaces. Formsof adiabatic potential sheets in the vicinity of crossings have been studied in the comprehensivepapers of Liehr (5052) and others (49, 5356). The exact vibronic levels of the modelE x e problemare easily obtained numerically (62, 79) by employing adiabatic basis of functions that are degenerate at the point of symmetry. Denoting the pair of diabatic functions ~, ±, where 0 ÷ = 0*_, the coupled vibrational equations are (in reduced units)
where p and ~b are polar vibrational coordinates and k is the linear z distortion constant. The energy levels Ware functions of D = ½k (the distortion energy) as shownin Figure 2. The eigenstates of this system are characterized by a good halfinteger quantum number j (79). This is a remarkable result that merits some discussion. Diagonalizing the electronic hamiltonian in the basis of the two diabatic
V
Figure 1 Adiabatic potential energy surfaces for a degenerate electronic state linearly coupled by a doublydegenerate vibrational mode. Coupling splits the isotropic paraboloid to give the familiar conical intersection of the linear JahnTeller E x e problem.
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NONADIABATIC DYNAMICS 283
states results in adiabatic functions:
i~er,1 .... :
[ ~ ei¢’/2~b + ei*/2~b_]. +
10.
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It is easily seen that these functions chanyesixth uponencircling the conical intersection in nuclear configurationspace, i.e. q5 , q5 + 2~. This is a general result (72, 8086). Since the complete vibronic wavefunction ~P must singlevalued, this implies that the associated vibrational amplitudes zupper.l .... mustalso changesign uponcircling the point of degeneracy.As a consequenceof this sign change, in the linear limit the internal rotation quantumnumberj can take on only halfinteger values (1/2, 3/2,...) stated above. Thedistinctive character of the level spectrumthat results has recently been confirmedfor the first time by direct observation (87). The occurrence of halfinteger quantumnumbersin systems without spin implies a topological or Kramerstype degeneracy, and is currently of interest in a wide variety of fields. For example, we note the growing literature on quantization (and fractional quantization) of the Hall conductance in twodimensional solids (85). Wilczek &Zee (84) have given a general discussion of the origin of fractional quantization, and derive a formula predicting halfinteger quantum numbers for twolevel systems (when adiabatic energies diverge linearly from the degenerate point). The appearance of halfinteger quantum numbers is important for the implementation of semiclassical descriptions of nonadiabatic phenomena.
2.8~~ 2.4
~

Fi#ure 2 Correlation diagram giving the relative energies of the exact vibronic levels of the linear E × e hamiltonian (Eq. 9) a function of the distortion parameter, 2. D = 1/2k
0.4I I I I I I 0.4 0.8 1.2 I I I I I I 1.6 2.0 2.4
Linear Coupling Parameter, D
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In series of papers, Mead(8890) and Mead& Truhlar (80, 91) examined the consequences of these general results in scattering and boundstate problems. Meadnoted that the form of the adiabati~ functions (Eq. 10) corresponds to a particular choice of yauye in the vibrational problem. It is possible to eliminate the sign change of vibrational amplitudes, but at the expense of introducing a vector potential term into the vibrational hamiltonian. This result has been termed the Molecular AharonovBohm Effect because of its formal similarity to the well known interference effect discussed by Aharonov& Bohn (92). The work of Mead and others shows that there are subtleties and surprises in the theory of vibronic interactions, and that care must be taken when assessing the validity of any approximation scheme(61). HigherOrder Effects and Localization
Several characteristic features of the linear case just described disappear when quadratic coupling or other symmetry lowering is allowed. These additional coupling terms are important for the E x e problem in vibronic states for whichthere are large vibrational displacements. There is both a loss of the free adiabatic pseudorotation of Figure 1, and a splitting of the degeneracies of states in which j (taken customarily to be positive unless otherwise noted) is 3/2 mod3. These effects have now been characterized experimentally by means of observedj = 3/2 splittings in trifluorobenzene cation (93) and the ion cores of benzene(94) and cyclohexane (95) Rydberg states. A quantitative account of the effects of higherorder coupling on the positions and intensities of optical transitions has been given for the ’ 3slE Rydberg state of symtriazine (87, 96). Inclusion of quadratic coupling terms in the E x e system leaves the diagonal matrix unchanged but alters the upper offdiagonal element to read: kpei¢, + 1/2gp2e2~¢,, 11.
where the parameter # measures the strength of the quadratic coupling. The corresponding adiabatic surfaces are
o~p~,~i/ E(p, ~b) = 1/2p2 ~ kp 1 +~l¢ cos (3~b) + ~~j
For small ratios, gp/k, the energies reduce to the simple form : 2 E = 1/2[p2 Tgp cos (34~)] T kp
12.
13.
to good approximation, and show directly the threefold symmetry. The splitting of degeneracies forj = 3/2 mod3 for small g is due to abovebarrier reflection in the threefold symmetric angular potential.
Annual Reviews www.annualreviews.org/aronline NONADIABATIC DYNAMICS 285 Asymptotically for large g the lowest state derived from j = 3/2 becomes degenerate with the ground j = 1/2 pair, corresponding to localization in three deep minima. A small energy gap between the near threefold degenerate levels, due to tunneling, implies strong localization and nearstatic distortions from the symmetrical configuration, in which case nonadiabatic effects are relatively unimportant. The magnitude of the tunneling splitting determines the time scale on which a measurement will show the molecule to be symmetrical. The concept of localization is of central importance in the interpretation of temperaturedependent ESR spectra of the alkali trimers X (9799). A uniform semiclassical treatment 3 of tunneling splittings for deep states in the E x e problemhas been given by Karkach & Osherov (100). ConeStates or Resonances in TwoLevel Systems
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The successful treatment of lowlying states of the conical intersections in terms of adiabatic approximations with correct boundary conditions suggests that a similar model might work for some higher states. In particular, there has been speculation dating from the work of LonguetHiggins et al (79, 101105) that somestationary states exist on the upper cone. [Thompson al (61) refer to these as "cone states" whereas loweret surface states are called "hatstates."] However,a thorough analysis by Sloane &Silbey (106) showedthat no exact wavefunctions are accurately described by states of the upper conical surface, and K6ppel &coworkers (107110)have extensively described the role of simple conical intersections in ultrafast electronic decay. Nevertheless, this idea remains attractive because it is knownthat in order to account for the facts of molecular spectroscopy, for some energy gap the adiabatic BornOppenheimer approximation must work well for excited states. Indeed, these very facts motivated Born & Heisenberg (111) and later Born & Oppenheimer(1) attempt to separate electronic and nuclear motion. The absence of simple resonant or cone states in the SloaneSilbey treatment has therefore not deterred further searching. Very recently, Thompson al (61) have found a close correspondence between exact and et adiabatic energies for large distortions and higher angular momentum states. They give, in addition, one exampleof an exact wavefunctionof the j = 5/2 type showingremarkable localization within the classical turning points of the upperconical surface. Sucha discovery, if shown be general, to has wide implications, because these states wouldbe regarded as precursors to the type of excited electronic states observed in conventional spectroscopy, and they should be semiclassically quantizable. This observation leads us to the final topic of this section, that of multimode nonadiabatic states and their relation to spectral complexity and irreversible electronic decay.
Annual Reviews www.annualreviews.org/aronline 286 WHETTEN, EZRA& GRANT Interactions and Radiationless
Multimode Vibronic Electronic Decay
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It is not possible to generalize very easily the above discussion to multimode systems (systems of two degenerate or degenerate plus nondegenerate vibrations) because of the occurrence of highly complexlevel spacings and coupled nuclear dynamicseven in deep adiabatic states. Some of the simplest unusual features were first described for trigonal molecules by Sloane & Silbey (106) and by Scharf &Jortner (112), but a full exposition awaited the work of Cederbaum, K6ppel and coworkers (46, 47). To see the source of the complexity, note first that the major changein the diabatic formulation above is in the offdiagonal elements, which for multiple modes become ~, k,p~ exp( i~b~), 14.
where{a} is the set of modes.The adiabatic energies are coupled to give the lower adiabatic surface : 2 ,Lk,p,22t2 ~ COS((~at~fl)1112
k,k#pap
#
where 2 are the ha~onic force constants of the modes. This evidently leads to highly correlated dynamicseven at lowest energies (motion in one mode "tunes" the conical intersection in another). For this lineardistortion approximation the surviving quantum number J is a sum of those from individual modesand takes on the halfinteger values characteristic of the twolevel electronic system. The di~culty of this problemis reflected by the facts that (a) even for only three modes, to obtain exact eigenfunctions pushes the limit of present computationalcapabilities, and (b) no solutions of the adiabatic approximation, Eq. 15, have been given. It is therefore necessary to seek statistical approachessuch as that suggested by Hailer et al (113, 114) or to look to semiclassical methods. Workin the latter direction is reviewedin the final section below. More generally, Cederbaumand coworkers have demonstrated success in multimode problems using the diabatic representation with potentials fitted to ab initio quantum chemical calculations (47, 76). Using the Lanczos method with simplifying assumptions derived from the precise spectroscopy of the situation at hand, they have been able to treat the previously intractable optical spectrum of NO:(114) and the photoelectron spectrum of C2H (109). Their work in this area represents an important ~ advancefor the interpretation of complicated molecular spectra. In C2H~, two spindoublet states are coupled by vibrations of the D2a
Annual Reviews www.annualreviews.org/aronline NONADIABATIC DYNAMICS 287 (conicalintersection) type, The surfaces in the spectroscopically observable zone are so widely split that it had previously been believed that the two photoelectron bands wcrc due to independent adiabatic states. Krppcl & coworkers’reassignment(109) establishes clearly that this is not the case. Moreover, model calculations show (107) that starting a nuclear wavepacket on the upper surface yields decay on a time scale of a single vibrational period, and offers no evidence for stationary states. The spectral line pattern in C2H~ very complex, and in the analogous is case for neutral NO2 statistical analysis has been carried out to showthat a nearest neighbor level spacing statistics are described quite well by the Wignerdistribution (115) [or, better, by a Brodydistribution (116)], found in the spectra of complex nuclei and nonlinear quantum systems whose classical limit is chaotic (117125). For these smallmolecule cases there is thus a strong connection between spectral complexity due to conical intersections and the "decay" or radiationemission behavior observed. K6ppel&Meyer(110) have pursued this point further in a recent paper exploring the connection among fluorescence yields, ultrafast decay, and nonadiabaticity as it appears most simply in doublet molecules (where spin interconversions are unimportant). Other than the apparent cone states uncoveredby Thompson al (61), as yet little evidence has emerged et from theoretical work for resonance spectra in nonadiabatic model problems.Clearly, this will be a major line of future work. In a similar vein, conical intersections are important in mediating chemical reactions or decompositions, and when manymodesare present a statistical theory is appropriate. Toward this end, Lorquet and coworkers (126128a) have generalized transition state theory to nonadiabatic states and applied it to +. decomposition of C2H~ the
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EXPERIMENTAL OBSERVATIONS ON THE STRUCTURE AND DYNAMICS OF NONADIABATIC STATES
The section above outlines howone can model potential energy surfaces, and, more importantly, calculate quantumstates in the vicinity of conical intersections. The formulation is general, but the specific case most easily treated is one in which the degenerate electronic term is well isolated energetically, with strong restoring forces preventing very large amplitude nuclear motions from the intersection. Such systems are most often associated with singlehole or singleelectron degeneracies. Quantum states derived from this simplest electronic configuration offer an excellent opportunity to probe the coupling of electronic and nuclear motion. The pattern of energy levels characteristic of a given system can be
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WHETTEN, EZRA & GRANT
understood with the help of correlation diagrams and a knowledgeof likely deviations from simple limiting cases. It now remains to ask what experimental methods can provide detailed information for a range of vibronic systems. Considering typical energy spacings between vibronic states, it is clear that optical spectroscopy is a prime candidate, with the most direct and unambiguousinformation coming from isolated molecules in a single specified initial quantum state. A sketch of the range of experimental systems for which nonadiabatic effects are found confirms this expectation.
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Survey of Nonadiabatic Effects: Rationale for an Experimental Approach The extreme sensitivity of vibronic states to perturbations has becomeone of the best known consequences of an electronic degeneracy. Both the relatively largeamplitude nuclear motions and electronic mixings are knownto be easily influenced by environment (129), as underlined by the sustained interest in the cooperative JahnTeller effect (130). This implies that if we hope to study the individual vibronic states, as opposedto bulk response properties of nonadiabatic boundstate systems, then it is essential that the molecule be isolated. The ground states of stable molecules contain an even number of electrons and are usually totally symmetric electronic terms. Openshell polyatomics of sufficient symmetryoften have electronic degeneracies, but as illustrated by work on metal trimers (60, 131), the reactivities of such systems generally require extraordinary measures in preparation and isolation. Many transition metal complexeshave degenerate ground terms, but most of these are observed only in the solid state and solution. Consequently, strong nonadiabatic effects are rare in the lower vibronic levels of the ground electronic terms of most molecules that can be readily isolated. At higher energies, near thresholds for chemical reactions or unimolecular dissociation, strong vibronic effects can indeed be expected. However,the associated surface intersections, although often critically important in the reaction dynamics of such systems (132), usually do not ¯ have high symmetryand involve complexand very large amplitude nuclear vibrations. Thus, one cannot look to ground terms of stable molecules as a source of fewstate nonadiabatic effects. Amongthe valence excited states of many molecules having some symmetry,a great numberinvolve degenerate or neardegenerate electronic terms. It is perhaps noteworthy that few of these known excited states have a settledupon interpretation (see for example11). By definition, valence states involve the strong interaction of at least two electrons or electrons and holes. In the spectroscopy of such systems it is also common both for
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the initial and final molecularorbitals to be degenerate, so that the excited state contains four closely related terms, two of which are degenerate. In such cases a description of the consequent vibronic coupling requires at least a fourstate treatment. Similar considerations apply to the ground states of cyclobutadiene and eyclooetatetraene, where the two highest electrons derive from the same degenerate molecular orbital (133). The extraordinary complexity of such (valence) multielectron degenerate configurations is reflected in the long history (134136) of effort on the lowest electronic transition in cyclopentadienyl radical CsH5. The ground state Of C5H5 the simple onehole configuration, (e~) 3, but its first has excited terms derive from the configuration (e~)Z(e~)1, which produces no less than eight coupled states from the threeelectron interaction. The numerousattempts to assign this spectrum serve as an indication of the complexityof degenerate valence states in general. Theeasiest wayto introduce a single hole in a set of degenerateorbitals is simply to remove an electron. The resulting ionic term has no inherent reason to be strongly coupled to any other, and recent experiments confirm that the spectroscopy of ionized states indeed offers one of the best opportunities for finding essentially pure twostate nonadiabatic problems in molecularboundstates (25, 26, 137, 138). Thus, it is not surprising that the most substantial experimental developments in the understanding of the twostate dynamic JahnTeller problem have come from advances in the spectroscopy of ions: vibrationallyresolved photoelectron spectroscopy (138140) and, more .recently, laserinduced fluorescence. The former has until very recently been limited by electron velocity resolution to offer only marginal separation of vibronic bands. The latter has great potential but most ionexcited states do not fluoresce. One of the major exceptions is the family of halobenzenecations that has been studied in great detail fromthis point of view over the past five years by Miller, Bondybey, and coworkers (25, 26, 137, 141144) and by Leach, CossartMagos, and coworkers (145148). Hexafluorobenzene cation has provided one of the most comprehensivetests of the twostate JahnTeller model to date (149), although its transition system still presents some difficulties, as one between valence states (in this case of the ion). On balance, valence complexities, together with the related problem of low fluorescence quantum yields, must be viewed as a fundamental limitation of optical spectroscopy as a general means for determining the vibronic structure of ions. Thus, the greatest longterm potential for the universal study of ion ground states appears to lie with photoelectron techniques, especially in their most recent form as laser multiphoton photoelectron spectroscopies (150152). It is nowbelieved that a resolution near 10 cm 1 will soon be possible.
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A simpler, entirely optical method of studying ions is through the spectroscopy of molecular Rydbergstates, in which one electron is excited to highlying orbitals of the Coulomb potential (153). To a good approximation, the excited electron has a negligible effect on the vibronic structure and dynamics the ion core (see below), so that the level patterns of accessed, and even the vibronic intensities, match those of the ionic state of the core. Until about eight years ago, however, the study of the vibronic structure of molecular Rydbergstates was extremely limited in scope. With the development of high peak power tunable dye lasers in the mid1970s camethe means to perform nonlinear spectroscopy on the highlying states of atoms and molecules. In this realm, particularly for multiphoton ionization spectroscopy, Rydberg state resonances play a featured role (154). It is therefore easy to see that the excitation to Rydberglevels molecules whose highestlying molecular orbitals are degenerate or neardegenerate offers a most promising means of studying twostate nonadiabatic phenomena. A major advantage of this approach is that, like photoelectron spectroscopy, the molecule is excited from the groundvibronic states of the neutral about which there is muchprior information. Thus, the nonadiabatic effects observed can be straightforwardly associated with the ionized state. The major advantage compared with the current practice of photoelectron spectroscopyis resolution; structure of the Rydberg state is probedat the nphoton resolution of the laser (typically m I cm1). To complete the connection between the Rydberg spectroscopy of the molecule and the vibronic structure of the ion, it remains only to justify the aboveassertion concerning the separability of the ionRydberg electron subsystems. Strong Vibronic Coupling in Molecular Rydberg States
An exceedingly simple and useful way to look at vibronically active Rydbergstates is in terms of a strong coupling limit for the degenerate ion core (155). In this limit the dominantvibronic coupling is that within the core, so that, neglecting rotation, the molecular ion and Rydbergelectron form noninteracting subsystems, except for the fact that the Rydberg electron is governed by the symmetric average field of the ion and is orthogonal with respect to core orbitals. This is clearly an idealized limit, and such a separation is only appropriate when the magnitude of the vibronic coupling in the core is muchgreater than both the dependenceof the Rydberg electronic energy on nuclear positions (for small amplitude vibrations) and Rydbergvalenceinteractions at the configuration level. For a given Rydberg state, the zerothorder vibronic energy levels appropriate to this separation are simply those of the cationic subsystem
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shifted down the Rydbcrgterm value. Bandintensities in optical spectra by of Rydberg states also find a match with corresponding photoelectron spectra: Within this limit electronic and vibrational moments separate, and the vibrational part corresponds precisely to the FranckCondonfactor expressionfor the set of transitions from the groundstate of the moleculeto the vibronic levels of the groundstatc ion. Symmetriesof these individual vibronic levels, though, arc a composite, determined by the direct product of the ion core vibronic state symmetry and the orbital symmetry the Rydbergelectron. One implication of this is of that nondeoenerate Rydberg states of a degenerate ion core will arise only as part of an electronic quartet, which remains fourfold degenerate in the idealRydberglimit. This results in a substantial reduction in the number of distinct Rydbergseries that can be expected, as degeneracies and splittings introduced by the Rydbergelectron are considered in a coupling hierarchy that proceeds on a eorevibronic, termbyterm basis. Recognition of this hierarchy, with its symmetry implications for optical transitions, is critical for the proper assignment of Rydberg states and associated vibronic structure in symmetric molecules. This spectral simplification is one consequenceof the idealized Rydberg limit and its approximate sum hamiltonian (155, 156). Other predictions include quantumdefects that carry for given series from convergence with one ionization potential to all others, and an excited state lifetime determinedsolely by radiative decay. Deviation from this limit with respect to these latter observables, whichin itself often constitutes a formof strong nonadiabaticity, is reviewed below. For the present, we turn to an examination of the completeness of this separation as a window the core on and the nonadiabaticity derived from its conical intersection. Structure of Nonadiabatic Bound States: Benzene and
Symtriazine
There are two general sets of criteria against whichone can easily judge the ideal Rydberglimit as an accurate predictor of the vibronic structure of degenerate core Rydbergstates. With an extensive data set spanning many series, the degree to whichvibronic structure conforms,series to series, with the highest available resolution photoelectron spectrum, together with the magnitudesof quartet splittings, will give one indicator of howfar Rydberg electroncore interactions carry the system from simple separability. Another test, for a vibronic system that is simple enough, is to check spectral positions and intensities within a single electronic state for internal consistency against the best available theoretical calculation. Benzeneand triazine in turn offer cases of each of these tests. At the same time these
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important systems provide interesting examplesof dynamical distortions in highly symmetrical rigid molecules, which by classical rules of bonding would be expected to retain high symmetry(133). BENZENE analogy to the halobenzene cations, we can expect benzene to By present a multimodevibronic coupling problem. This is confirmed both by twophoton Rydberg spectra (94, 156158) and moderately wellresolved conventional (159) as well as laser photoelectron spectra (150). This makes a definitive confirmation and interpretation of observed vibronic structure by direct calculation difficult. However, size of the data set the combinedwith the availability of the photoelectron spectrum provides the meansfor a test of the first kind. In conformity with ideal expectations, degenerate Rydbergstates of this system that arise in zeroth order as products of the degenerate core with nondegenerate Rydberg orbitals (for example nsa~g), show readily assignable structure in JahnTeller active and symmetric modes, and this structure is virtually identical to that of the photoelectron spectrum. Rydberg states derived from degenerate hydrogenic orbitals provide an even more sensitive test. As noted above, in the limit of vanishing Rydbergcore interaction, the simple product of orbital with coredegeneracy will double the degeneracyof all such vibronic levels. A great many these are of accidental degeneracies, and any perturbation (configuration interaction or vibrationRydberg coupling) will strongly mix zerothorder states and produce characteristic splittings. Such splittings are observed, but with one exception all are exceedingly small (156). Typical is the 15 cm~ splitting of the E2gAlgcomponentsof the 3d~ origin. The exception is the 3px origin, for which the measured splitting is 160cm ~ (94, 157, 160), a value that perhapsreflects the special significance of this state as derived from the lowest degenerate Rydberg orbital. This generally favorable picture of the idealRydberg limit for the vibronic structure of benzene Rydberg states is supported by the small magnitudes of other deviations, such as origin perdeuteration shifts and trends in vibrational frequencies. Thus, it is with reasonable confidencethat the Rydberg data can be combined with the specific though much lower resolution photoelectron spectrum to provide a qualitative picture of vibronic coupling in the 2Elo C6H ion matching in completeness that for ~substituted benzene cations. Main conclusions at the current level of understanding are as follows : 1. The dynamicalJahnTeller effect in the 2Elg benzenecation is inherently multimode, involving at least JahnTeller modesv6 and v9. In benzeneh6, v6 dominates, with a total stabilization energy of about 250 cm
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Greater apparent v9 activity is seen for d6, a result consistent with multimode coupling expectations (106). In both eases the number active modes far smaller than that for the halobenzenecations. is 2. Higher order JahnTeller effects are quite small, leaving singlemode vibronic angular momentum largely unquenched. 3. A Renner effect in the outofplane mode v16 has been observed and characterized for the first time (94, 161). The observation of interferences in combinationstates with JahnTeller active v6, as predicted by theory (162), sheds further light on multimode quenching and coupling vibronie angular momentum nonadiabatic states. in SYMTRIAZINE twophoton absorption spectrum of symC3NaH The 3 showsa set of sharp vibronic bands associated with a clear origin (To 55,791 cm 1 ; 55,882 cm1, _ d3) (87). Thesebands, pictured for triazineha ’, in Figure 3, are readily assigned to the lowest 3s~E Rydberg state. Withits totally symmetric Rydberg orbital and degenerate ion core, the limiting picture just confirmed for benzene predicts this state to be JahnTeller active. Analysis showsthat it is, with coupling dominated strong activity by in a single normal coordinate, the lowest frequency e’ mode, Vr, a ringbending vibration. This simplicity presents a unique opportunity. All other known examplesof nonadiabatic states for which resolved vibronic spectra have been recorded for isolated molecules are multimodesystems. With its strong singlemodeconical intersection, the 3slE’ state of triazine offers a chance to (a) visualize the dynamics of nonadiabatic bound state vibronic motionin an active vibrational space of manageable dimensionality, and (b) quantitatively test the fewparameter numerical coupling theories reviewed above, from which can also be obtained accurate vibronic wavefunctions. Comparisonof the spectrum in Figure 3 with the correlation diagram in Figure 2 showsthat a description in terms of simple linear coupling with k ~ 2.2 gives a good account of level positions through the conical intersection and above, thus allowing the confident firstorder assignment of all the bands of the spectrum. Linear coupling alone, however, fails to predict the observed intensities (the spectrum shows strong bands that wouldbe forbidden for strictly linear coupling) and certain distinctive splittings. Inclusion of quadratic terms with g = 0.046 and optimization of k to 2.14 gives quantitative and sensitive agreementwith both positions and intensities of all measured bands(96, 163). Withthis coupling strength, the zeropoint and first few excited levels of the active mode,v6, lie substantially belowthe conical intersection. Simple calculation shows that the exact level structure for such conditions is reasonably well described by the eigenvalues of the adiabatic lower surface BornOppenheimer (or more correctly BornHuang) hamiltonian. Motion
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in these lower states can thus be viewed in very simple terms, as approximately that of a free internal rotor built on a radial harmonic oscillator with a level structure (79) E(v,j) = o~(v 1/2) + Aj2 16. where ~o is the fundamentalfrequency and A is the rotational constant. The latter term is determined by the amplitude of the trough, Po = k/2, via A = hz/2rnp2o, where for the present case Po = 0.26/~ and A is calculated to be 80 cma. Importantly, it is found that this rotational constant gives a precise account of the deepest few rotor states, so long as the angular momentum quantum number j is taken to be a halfodd integer. This observation constitutes the first direct confirmation of the appropriateness
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56.300 56600 56900 57200 57500 57800 1) TWOPHOTON ENERGY (CM ’ Figure 3 Twophotonabsorption spectrum of the 3sXE Rydberg state of symtriazine. The stick fioure indicates theoretical positions and intensities for bands assigned in terms of approximatej quantum numberas : 1/2 (origin), 5/2, 1/2, 7/2, 5/2, 1/2, 11/2, reading from the left. (Cf Figure 2; 3/2 bands are forbidden. These and symmetric fundamentals and combinations are suppressed.)
55400 55700
56000
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of the choice of phase implied by the electronic basis functions of Eq. 10 in forming the proper adiabatic limiting wavefunctions. It is interesting to note that the energy of the first excited state of this adiabaticlimit pseudorotation is 160 cm’, which corresponds to an extraordinary low frequency of 5 x 1012 sec1 for internal motion in a molecule as rigid as triazine. The level structures predicted by each of the modelsdiscussed here are summarized,together, with experiment, in Figure 4 (96, 163). 6OO 4OO
I1~_~
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AFR
LJT
L+Q
Expt.
200
.
0
zoo E ~ 400
~ 600 I
....... ~/~ "’...
"~""
z 800
.%_~
~ooo %
....
~/z
~.
1400
1600 Figure 4 Comparisonof vaNouspredictions for the level structure of 3s~’ symt~azine with experiment. Fromthe left are: (a) the adiabatic fr~rmor model(Eq. 16), (b) linear J~nTeller, and (c) linear plus quadratic JahnTeller coupling. Dashed lines connect states of (approximately) like vibrational angular momentum.
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This essentially twoparameter of the entire spectrumis significant : fit 1. It offers the most direct and dramatic confirmation yet of the classic theory formulated over 25 years ago by LonguetHiggins and coworkers (62, 79). 2. It decidedly confirms the idealRydberglimit (155) for the interpretation of vibronic coupling in molecular Rydberg states; vibrationRydberg interactions, if present, are beneath the resolution of the correspondence between theory and experiment.
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The adiabatic potentials derivable from this calculation must be regarded as very nearly exact to an energy at least as high as the highest measured eigenvalue. It is interesting to compare the potential in the pseudorotation coordinate around the bottom of the trough with the internal rotor levels built on the first radial oscillator state. As Shown in Figure 5, the quadratic barriers to pseudorotation only weakly alter the shape of the potential surface. Despite this, and reasonably close correspondence between linear and linearplusquadratic eigenvalues, evident splittings and transfers of intensity showthat, in the vibronic hamiltonian, these quadratic terms have a significant effect on the wavefunctions. With near quantitative correspondence between experimental and
j=7/2
j=5/2 j3/2
j~/2
~ 0.00
0.78
1.57
2..35 3.14 3.92 4.71 PSUEDOROTATION PHASE.RADIANS
5.49
6.28
Figure 5 Adiabatic potential in the pseudorotation coordinate ~b as calculated from Eq. 13. The horizontal lines give the lowest five levels in the JahnTeller pseudorotation mode.
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theoretical intensities, wavefunctions can be derived with reasonable confidence from the present calculations. These are conveniently visualized as nuclear probability densitics (5861). Figures 6 through 8 showplots nuclear probability densities (for complexvibronic wavefunctions) for the first four levels in thcj = (+ 1/2) mod manifold. For the first two states 3 scc that quadratic coupling modulates the nuclear probability densities (which are cylindrically symmetric for linear coupling alone). Nuclear density accumulates over surface depressions or saddle points. The states with the unusual density pattern shownin Figure 8 are a closelying pair labeled byj = 1/2 and 7/2 in the linear limit, which repel by mixing due to quadratic terms. To summarize, symtriazinc presents unprecedented simplicity in an isolated nonadiabatic system. With its single active modeand large linear
’ Figure Nuclear 6 probabilitydensityfor the ground vibronic state of 3s~E symtria~ine calculated I Z +12+ 2 (see Eqs.9 and11)for coupling as IZI parameters correspondingthe to theoretical levelstructure Figures and andintensities Figure of 4 5 of 3.
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’ Figure 7 Nuclear probability density for the second excited vibronic state of 3a~E aymtdazine [the lowest ~xcited state of thej = 1/2 rood (3) block], as in Figure
stabilization, it is possible to visualize easily the dynamics its vibronic of pseudorotation in the adiabatic limit. From the precise correspondence between high resolution jet spectroscopy and theory, when carried to second order in coupling terms, there emergesa quantitative picture of the role of quadratic effects and the loss of cylindrical symmetry splitting and in mixing vibronie levels. SlowElectron Systems: Nonadiabaticity in the Failure of the IdealRydber~l Limit and Related Systems Rydberg states of symmetric molecules provide a convenient view of the vibronic structure of degenerate ion gores. More universally, Rydbergmoleeular core assemblies also constitute a class of systems for which commensurate electronic and nuclear frequencies are readily attainable. Such states are
ACCIDENTAL RESONANT MIXING IN MOLECULAR RYDBERG STATES
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very important, dominating the resolved absorption spectrum of most molecules beginning at. energies above twothirds of the first ionization potential. As mentionedabove, the novel feature of such states is that one electron has escaped from the molecule and now"sees" it predominantly as a rigid ion or even a point charge. The level spacing for this electron reflects its delocalized, hydrogenic character, and can be represented by the formula
2 = R(n~) E(n)
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17.
where R is the Rydbergconstant, n a principal quantumnumber, and 6 the quantum defect, which is correlated with the orbital angular momentum and nearly independentofn (164). Adherence this zeroth order picture for to the case of a degenerate core reveals the nonadiabatic boundstate structure of openshell molecular ions. Deviations constitute a second important class of nonadiabatic interaction. Three kinds of nonadiabatic interactions can be envisioned : 1. Levels of the same n but different 6 (different series) can be coupled vibration or, for very high n, by rotation. For vibration, Rydbergnuclear interactions decrease as na, so that significant splitting should be expected only for lower Rydberg states. It is also necessary that appropriate excited vibrational levels of the lower energy series overlap lower levels of the upper state. These two factors tend to confine strong vibrational couplings to levels of intermediate n. For example, consider the s and d Rydbergorbitals of benzene (156), l(6), which are s(0.76), do(0.05), and dr(0.12). At n = 3, 3s3do3dt spacings are 9000 and 2000 cm 1. Only high vibrational overtones have such energies, and these should be only inefficiently scattered by the Rydbergelectron, so one might expect the adiabatic approximation to be fairly successful. At 1. the n = 5 level, however, the spacings are 1900 and 400 cm Fundamental vibrations of the correct symmetryare in this range and readily mix the two hydrogenic states. 2. More generally, strong interaction can occur whenever fundamental vibrational frequencies of proper symmetrytype match the gap between Rydberg states of different principal quantum number n, for example ns ~* (n 1)do as observedin benzene(156). 3. As another form ofnonadiabatic coupling in manymolecules, the lowest Rydbergstates having electronically excited cores (excited ionic states) lie overlapped with higher Rydberg states converging to the first threshold. As with 1, examplesof 2 and 3 have been observed (156). Such occurrences can help confirm symmetryassignments of highlyexcited molecular states.
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Of more interest from the present point of view, they also provide direct information on the mixing of fast internuclear and slow electronic oscillations. The first molecule to be considered from this viewpoint was H2, by Berry &Nielsen (165). Theseauthors gave a general theoretical formulation in the adiabatic representation in which they constructed electronic wavefunctions and potential energy surfaces, derived the corresponding vibrational states, and finally evaluated the matrix elements of the kinetic energy operator that couples the BornOppenheimerstates. This procedure, in principle, yields exact energylevels (exclusive of rotation). It is, however, exhaustive theoretical treatment that is difficult to reproduce for more complex molecules. Among important results is the identification of the zones of strong mixing (166). As discussed in the next subsection, the systematics of these zones can be understood in a very natural way. It is instructive to look at the interactions betweenRydberg electrons and core vibrations from a dynamicpoint of view. Consider the picture in which a shortpulsed radiation field prepares a coherent state consisting of a particular Rydbergorbital and corevibration. For a twostate interaction this state would begin to mix with one consisting of the other Rydberg orbital and core vibration pair. The Rydberg electron in effect inelastically scatters off the core. In a strictly twostate picture this mixingleads to a’ simple pattern of quantumbeats, and a higher resolution, longer time experiment would reveal the two mixed eigenstates of the interaction separated by the beat frequency. Weakerinteractions dephase these beats and produce an apparent broadening of the individual eigenstates of the twostate interaction. Dynamically the relaxation becomesmore complex, with the resulting states not well described in terms of any zerothorder separation into ion normal modesand hydrogenic orbitals. Rather, in timedependent language, the system evolves to a vibronically mixed (randomized) core in which complicated, large amplitude nuclear motion strongly couples the possible final electronic states. In recent nonlinear absorption experiments on ultracold molecules, Whettenet al (156) observed several pronounced examples of this type nonadiabatic interaction in benzene. These include at least one of each of the three types of interaction described above, including apparent coupling betweenthe coreexcited 3s Rydbergstate converging to the second IP, and neighboring (zerothorder) 1 and 5dl st ates onthegrou stat e core. In nd dynamical language this latter case provides an exampleof coreelectronic inelastic scattering of the Rydberg electron. An equally dramatic example is found in the high angular momentum states of H (167, 168). In the 50 orbitals of 2, m olecular r otation i s 2 sufficiently fast compared evolution among electronic states that the to the
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latter uncouple from the axis, producing a smaller splitting on each rotational state of the ion core. These were detected by the 5g4f infrared emission, and explained by an angular momentum coupling model. [High angular momentum states of benzene have also been observed (156, 157), but it does not appear that this inversion of term spacings occurs, since the rotational spacing in benzene is muchsmaller.] This is an exampleof an inverse adiabatic situation whereit is nowthe vibrational spacings that are largest. Sucha situation is highly counterintuitive, but is to be expectedfor manysystems, particularly those involving electronic fine structure (in photodissociation, for example).Starting from this point of view is essential to understand the term splittings in the Rydberg spectrum of benzene, where, as discussed above, it is best to construct electronic levels on a vibrational state of the ion; the opposite approach leads to qualitatively incorrect expectations(155). In these cases it is essential to avoid associating a distinct adiabatic surface with each electronic term. Moregenerally, the occurrences of regions of strong mixing are readily predicted in terms of known level spacings (vibrations and rotations of the ion, Rydberg electronic spacings) (169). Furthermore, the information highly redundant because the wavefunctions producing the zerothorder pattern of levels are assumed known.Thus, for example, the knowledgeof the strength of interaction coupling the v16 vibration of benzeneto the 5f and 5d hydrogenlike electronic orbitals predicts the strength of this interaction for all other n (156). The correct meansof taking this knowledge into account is via the multichannel quantumdefect theory (MQDT) (166, 170). This results in an enormous simplification of the description of these interactions. It is based on the electronion scattering problem,facilitated by use of the asymptotically correct Coulomb potential, so posed as to allow the experimental data to solve the configuration interaction and nonadiabatic problem at the same time, yielding directly the nonadiabatic interaction matrix elements with minimal assumptions. Application to molecules has been concerned primarily with NOand H2, especially in the latter case with regard to rotational channelsof interaction, but is readily extendedin principle (171, 171a, 172). Verydifficult regions the spectra of these molecules have yielded to this approach, which also offers the simple scattering interpretation of nonadiabatic dynamics discussed above. An understanding of the nonadiabatic interaction of weakly bound electrons with vibration and rotation is extremely important in the decay and ionization properties of molecularsystems. To see this, let us consider again the interaction in which an electron is scattered into a lowerlying orbital via excitation of a corevibration. Imagine, as above, preparation of the coherent state consisting of
RADIATIONLESS DECAY AND AUTOIONIZATION
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the zerothorder n! orbital; vibrational interaction mixes it with another state (n1)1’, which in effect serves as a doorwayto a more dense set of overtones associated with lower Rydberg states. At some stage an essentially continuous manifold of lower levels takes over, and one has a Lorentzian linewidth corresponding to exponential decay. The Rydberg states of benzene (156158) taken at rotational temperatures near 0 K provide an example of precisely this coupling hierarchy. Pairwise mixings have been discussed above. Moreover, where several states of proper symmetrynearly coincide, one has higherorder mixings. Finally the homogeneous linewidth of each identifiable band reflects strong coupling to the quasicontinuum structure beneath. This latter aspect is confirmed by direct timeresolved experiments using femtosecond laser pulseprobe techniques carried out by Wiesenfeld & Greene (173). 1 bandwidth of 100 cm excites a superposition, which decays exponentially, as probedby timeresolved ionization. Significantly, for both benzene and toluene, the agreement between dynamical (173) and spectroscopic measurements (156, 157, 174) is quite good, thus giving credence to the idea that the final irreversible decayproductis a set of states with energyin large amplitude vibrations, states that cannot be ionized by a visible laser. Thus the width of the homogeneous line is that corresponding to the net process by which the electron spirals inward, transferring energy to the core. The widths or decay times measure the strength of interaction between the backgroundstates and the pure electronic excitation, and as might be expected this coupling strength decreases rapidly with n. This idea can be carried to an extremeto predict that Rydbergstates of very high nl numbers have extremestability; they are effectively metastable because of the rarity of a collision betweenthe Rydbergelectron and the ion core. With very low transition frequencies, radiative lifetimes are also very long. Some evidence for this behavior has been gathered by Freund (175). Multiphoton excitation with circularly polarized light could well offer an effective spectroscopic meansto produce these states. Similar arguments apply to the phenomenon autoionization, but these of are resonances in which the reverse flow (energy from vibrotation to electronic) occurs. For the case of diatomics this manifestly nonadiabatic process has been studied within the MQDT formalism (176), but explicitly timedependent experiments have yet been attempted. NEGATIVE In principle a similar treatment could apply to negative ion IONS states, but all the nice features of the Coulomb potential applicable above are not in force here. Spacelimitations preclude consideration of the highly interesting topic of resonant scattering here. Nonetheless, a point regarding autodetachment is worthy of mention. The recent experimental observation of electrondipole bound states
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gives a picture of autodetachment that is evidently related to rotational predissociation (177, 178). Onecan view these states in terms of the electron cycling about the positive end of the dipole, so weaklyattached as to have only one bound state for most if not all angular momentum states of the core. With the detached neutral molecule as a core, resonances above threshold are analogous to the case of a Rydberg state excited above the adiabatic IP. Here the core gives up very little rotational energy to detach an electron, yet the resonancesare fairly longlived.
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CLASSICAL AND SEMICLASSICAL APPROACHES TO NONADIABATIC PHENOMENA
As is apparent from the preceding discussion, the interaction between theory and experiment has played an important role in developing an understanding of vibronic states of molecules in which a doublydegenerate electronic state is coupled to one or a very small numberof active modes. For such systems a full quantum variational treatment of the vibronic hamiltonian is feasible, so that model parameters can be determined to provide the best fit to experimentaldata (e.g. symtriazine). The size of the associated secular determinant, however, grows extremely rapidly with the number of active modes, and there are no useful decoupling approximations that can be applied. Hence, the limits of current quantummechanical technology are reached very quickly for problems involving only a modest number of modes. Although procedures such as the Lanczos algorithm (179) or the related RecursiveResiduemethod(180) have great potential solving very large eigenvalue problems, and although a statistical approach maybe appropriate for describing vibronic level structure in highlyexcited dense manifolds (113, 114), the situation described above points to the desirability as an alternative of a semiclassical (asymptotically valid as ~ 0) theory of vibronic level spectra. Sucha theory wouldideally provide both a quantitative treatment ofvibronic spectra in the multimodecase and a conceptual frameworkfor obtaining qualitative insight into manifestations of vibronic coupling; it would therefore be an extension to multisurface phenomena the various semiclassical approaches that have of been successfully applied to single surface scattering and bound state problems. A semiclassical theory of multimode vibronic phenomena as just described is not available at present. Despite an enormousamountof work on the generalization of semiclassical methods to treat nonadiabatic processes occurring in collisions, the general problem involving multiple (> 2) interacting surfaces, strong and delocalized nonadiabatic couplings,
Annual Reviews www.annualreviews.org/aronline NONADIABATIC DYNAMICS 305 and manynuclear degrees of freedomremains essentially unsolved. It is our purpose here to review a small body of work that is in our view .likely to provide a foundation for future theoretical treatments of problemsrelevant to the recent experimental advances described in previous sections. Thus, we consider some recent classical and semiclassical approaches to radiationless transitions and boundstates in JahnTeller systems. Most of the work we describe is within the frameworkof the "classical electron model" of Miller, Meyer& McCurdy; this model is therefore described in somedetail. In order to place this work in a proper complete context, it would be necessary to give a thorough discussion of all the major lines of development in the semiclassical theory of nonadiabatic phenomena(a huge literature). Westop short of this, presenting instead a few pertinent references. Reviewsof manyaspects of the subject can be found in Miller (181), Lain &George(33), Tully (17), Child (3032), Nikitin (28), Ziilicke (29), Kleyn, Los &(3islason (39), Rebentrost (36), Ranfasni (182), Crothers (34), Ovchinnikov & Ovchinnikova (15), Heller & (183), Nakamura (184). Background A central issue in the theory of nonadiabatieprocesses is the extent to which "classical path" descriptions are meaningful or useful. That is, to what extent can the heavyparticle (nuclear) degrees of freedom be taken undergo classical motion in an effective potential determined in some fashion by the quantal dynamics of the coupled electronic degrees of freedom? A pathintegral formulation (181, 185187) of the nonadiabatic scattering amplitude enables a formal answer to be given to this question: Theexact (semiclassical) effective "potential" is of necessity nonloeal in time and must be determined iteratively. This result clearly implies insuperable practical difficulties unless other, perhaps uncontrollable, approximations are introduced. Further work in this direction has led to the widely used MillerGeorge (188) and TullyPreston ("surfacehopping") (189, approaches, whereas the selfconsistent matrix propagation method of Freed & Laing (191193), further developed by Herman& Freed (194), closer to the original pathintegral approach. At a simpler level, the classical motion of the nuclei can be taken to be determined selfconsistently through interaction with the electronic subsystem. The nuclei then provide, through vibronic coupling terms in the complete molecular hamiltonian, an effective, timedependent electronic hamiltonian, whichinduces transitions in the manifold of electronic states of interest. Thetimedependence the electronic state in turn gives rise to a of timedependent, effective (Ehrenfest) potential for the nuclei through the
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expectation value of the nuclearcoordinate dependent molecular hamiltonian in the instantaneous electronic state. A specific exampleof this selfconsistent coupling is treated in the next section. Considerableeffort has been devoted to assessing the validity of classical path methods in general (195, 196). For a system with a single nuclear degree of freedom and a localized crossing of two adiabatic curves, it is necessary that (a) the form (i.e. slope) of the potentials be similar in region of the crossing, and (b) the nuclear kinetic energy be large compared to differences in the two potential surfaces in the interaction region. In addition, the usual conditions for semiclassical treatment of nuclear motion should hold. Despite such stringent requirements, the selfconsistent coupling approach underlies a substantial amountof work in the area. See, for example: Ehrenfest equations (200202); firstorder selfconsistent Eikonal method (197199); Dynamical HellmanFeynmantheorem (203); timedependent HartreeFock theory (204, 205); dynamical vibrationelectronic coupling (206). In particular, the classical electron model Miller, Meyer& McCurdy (207211) has the selfconsistent formulation its starting point. Nevertheless, severe conceptual difficulties and inconsistencies are inherent in such a mixing (albeit selfconsistent) of classical and quantal dynamics. For example, in a system that is asymptotically in a superposition of two electronic states, the nuclei execute some averaged dynamics, as opposed ~o motion determined by one or the other adiabatic surface, as might be expected on physical grounds. The classical electron picture is intended to surmountsuch problems, and to facilitate treatment of resonant processes in electronicvibrational and electronicrotational energy transfer (212). Review of the Classical Electron Picture The classical electron model of Miller, Meyer & McCurdy,which is an attempt to overcome some of the difficulties of mixed dassical/quantal dynamics, works in the following way [we do not discuss the related but apparently less general Spin Matrix Mapping (210) and Classical Pseudopotential (208) approaches]: For a system in which there are coupled electronic states of interest, the electronic hamiltonian can be represented as an N × N matrix whose elements depend on the nuclear coordinates {Q~} : Hkk,(Q) k,k’= 1 ..... N. 18. Adiabatic electronic representation is used for simplicity, but it is also possible to formulate the theory in the adiabatic basis (209). If the nuclear coordinates Q(t) are taken to be given functions of time, the timedependent
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Schr6dingerequation for the electronic wavefunctiongives rise to a set of coupledequations for (a~(t)}, the coefficients in the diabatic basis ihdk = ~ Hkk,(Q(t))ak,.
k"
19.
A key step is nowthe change of variables [of a type originally due to Dirac (213)3 ak i°k,n~/2e =20.
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giving the polar decompositionof the complexcoefficients amplitudes (nk) and phases (Ok}. Note: 0<nk<l , ~nk1. Defining the "hamiltonian’ h(n, 0; Q) = a* k,kIIkk,a
kk’ = E ~1/2~1/2t/ kk" °i(OkO~’)
(ak}
into (real) 21.
22. 23.
as the expectation value of H in the electronic state, the remarkableresult is obtained that the quantummechanical set of coupled equations is entirely equivalent to "hamilton’s equations" for the canonically conjugate pairs
(n~, 0~):
fik Oh 0=Oh = 00~’ k = 1,..., U. 24.
[This equivalency obtains because mappingsof type, Eq. 22, for arbitrary matrix operators transform commutators into Poisson brackets (209).] Addingthe classical nuclear kinetic energy then gives a completelyclassical, timeindependent hamiltonian ~,~ that determines the selfconsistently coupled nuclear/electronic time evolution through the classical equations of motion for the nuclear degrees of freedom, together with Eq. 24 : p2 25. 9~(P,Q,n,O) Y’,~~ +h (n,O;Q)
zm~
/~,
= oO,’
~,=
26.
This time evolution preserves both total energy and electronic probability
~, n k.
For the limit of a singlesurface problem, [nxl = 1 and Eq. 26 simply reduce to the classical nuclear equations of motionfor the potential surface
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308 WHETTEN, EZRA & GRANT
V(Q) =h(nl, OI;Q). In the general twostate case, the classical electron hamiltonian is ~J~ = ~ P2~/Em~ (1  n)H~+ nil22 + + 2In(1  n)]
1/2H12 (cos 0)
27.
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where a canonical transformation has been made to new variables n’ = nl +n2  1, n ~ n2, 0’ = 01, 0 = 0201, so that only the relative phase 0 appears. For the simplest twostate linear E x e JahnTeller problem (cf previous section), the classical analog hamiltonian in the diabatic representation is : ~/2. 2 P~ +p2/2+2kp cos (Oqb)[n(1n)] 28.
At this point all that has been achieved is an elegant reformation of the Ehrenfest force classical path equations. The major innovation in the work of Miller, Meyer& McCurdy the realization that the classical analog is hamiltonian can be used within the context of the classical Smatrix or quasiclassical trajectory approaches to determine nonadiabatic transition amplitudes, provided the following "Langer modification" is made: n~ ~ n~ + 1/2, 29.
together with a change in the form of ~ that maintains equality between the semiclassical electronic eigenvalues and adiabatic potential surface energies. The substitution of Eq. 29 ensures that there is a nontrivial dependenceof the final electronic action uponthe initial electronic phase. [For a justification of the Langer modification, see the discussion by Herman & Currier (209a).] The resulting modified hamiltonian for general twostate systemis : ~/g’ =~ P~/2rn~ (1  n)II1 ~ +nIt 22 + +2[(n+ 1/2)(3/2n)]I/2H12 cos 0. 30.
Applications of the general twostate classical analog hamiltonians, Eqs. 27 and 30, and the linear JahnTeller hamiltonian, Eq. 28, in particular, are reviewed in the next section. Applications of Classical Electron and Related Models
NONADIABATIC PROCESSES IN COLLISIONS The
classical electron (Ehrenfest with Langer modification) and related classical pseudopotential and spin matrix mapping methods have been applied by Miller and coworkers to a variety of electronically nonadiabatic collision processes : quenchingof an
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excited finestructure state of the fluorine atomF*(EP1/2)by collision with H + or Xe (208); quenching of F*(2P1/2) by collision with H2 (ER energy transfer) (210); quenching of Br*(2P1/2) by collision with n2(v = 0) transfer), for collinear (214) and threedimensional (215) systems; charge transfer in Na + I collisions (216). In all cases where corresponding closecoupled quantumcalculations are available for comparison, there is encouraging agreement betweenthe exact results and quasidassical trajectory calculations of cross sections and transition probabilities. In particular, resonant features are correctly described using the classical analog methods. There is clearly tremendous scope for application of these techniques to nonadiabatic processes already tackled using the popular trajectory surfacehopping method(189, 190), and for quantization of the theory using the classical Smatrix formalism. BOUND STATES line In with emphasis inpreceding the laid sections this of review nonadiabatic on cffects molecular in bound states, proceed wc to consider in somedetail fewapplications to dateof the now the made classical electron picture these to problems. anapproach potentially Such is very fruitful, much and remains bc done this to in area. Ultrafast nonradiative decay via conical intersections In a pioneering quantummechanical calculation, K/Sppel (107) modeled the ultrafast internal conversion between .~ ~ .~ states of C2H~.The modelsystem was taken to be two neardegenerate states in the diabatic representation coupled by a single nontotally symmetric mode, together with two totally symmetric modes. Such a system has a multidimensional conical intersection, since the totally symmetricmodes"tune" the electronic energies. The timedependent probability of being in the upper (diabatic) state (summed over all vibrational states) after sudden excitation from the neutral molecule ground vibrational state was computedby direct integration of the timedependent Schr6dinger equation. The key result to emergefrom this calculation is the extremely short time scale (~ 101’~ s) characterizing the radiationless decay. The necessity for coupling of the electronic states via more than one vibrational mode,hence the existence of a conical intersection, is borne out by a single mode calculation having revealed no rapid internal conversion. The disposition of energy amongvibrational modesin the electronic ~ vibrational energy transfer from the ground vibrational state of the upper diabatic electronic state was also calculated. It is natural to consider the applicability of the classical electron modelto this type of problem.In fact, Meyer(217) has recently investigated the same systemas K6ppelby using an Ehrenfest classical analog hamiltonian, set up in the way outlined above. Using the classical histogram method for
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assigning electronic states, and taking the initial state used in (107) correspond to an ensemble of trajectories, remarkably good agreement betweenclassical and quantummechanical probabilities is obtained for the threemode problem. Reasonable but "less beautiful" agreement is obtained for model two and onemodesystems. This is in accord with the general principle that classical calculations are most reliable when some averaging (in this case, over vibrational states) occurs. The enormous potential of the classical electron modelin this context is apparent when it is realized that anharmonicmodesor several additional vibrational degrees of freedom are easily included, while quantummechanically such systems remain intractable. Meyer’s calculations showthat mode anharmonicityhas little effect on the shorttime (t < 40 fs) decrease of the probability of remaining in the upper state. Quenching of regular oscillations of P(t) occurs, however,at longer times. Increasing the number of modesto ten, for example, has very little effect on the timedependent probability (a tenmode quantal calculation is of course well beyond presentday capabilities), Finally, a recent comparison (110) of exact quantum and classical analog results for the timedependent photon emission rate from a twolevel twomodesystem shows reasonable overall agreement with quantum calculations. The classical electron model thus represents a computationally convenient and tractable approach to multimode vibronic bound state problems, and considerable development along these lines can be expected in the future. One advantage of a completely classical formulation of the vibronic problem is that examination of trajectories can provide insight into complicated vibronic dynamics. In the next subsection we describe somerecent calculations in which the classical electron picture is used to study boundstates of linear JT systems. Bound states of linear JahnTeller systems Wenow briefly survey the results of our investigations of the classical analog hamiltonian for the linear E × e JahnTeller bound state problem; details are given elsewhere (J. W. Zwanziger al, submitted for publication). The hamiltonian Eq. 28 et that for a multidimensional nonlinear classical dynamical system. In line with muchof the recent research in this area (218), we emphasize the qualitative appearanceof trajectories, Poincar6 surface of section plots, and the possibility of both quasiperiodic and chaotic motions. The relation between quantumand classical integrability for a twostate ("electronic") system interacting with a boson ("vibrational") mode has been studied using several approximations to the exact dynamics (219), including the selfconsistent coupling formulation. Judd (48, 220) has recently described JahnTeller trajectories for several systems. It should be noted that Judd’s work goes only as far as the
Annual Reviews www.annualreviews.org/aronline NONADIABATIC DYNAMICS 311 determination of nuclcar trajectories on particular adiabatic potential sheets, so that treatment of the selfconsistently coupled dynamics described by Eq. 28 represents a considerable extension of this approach. The hamiltonian Eq. 28 leads to six coupled equations for the variables (pp, p, pC, ~b, n, 0). Initial values of the pair (n, 0) can be chosen correspond to to starting on either adiabatic sheet, or diabatic state, etc. 0Notethat wcdeal here only with the Langcr unmodified hamiltonian Eq. 28.) The complexity of the problem can bc reduced by noting that ~ is a 1. l resonance hamiltonian, since the angles 0 and ~b appear only in the combination(0~b). Transformingto newcanonical variables (Pp, p, It, ~1,12, ~b2) wc obtain hamiltonian ~ independent of ~, so that Ix is a constant of the motion: ~=P~
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~ + ~ + ~ E~ +~/~
+kp[(I2+I~/2)(1+I2I1/2)] ~/~ cos ~z" 31.
p~
1
Wetherefore have effectively a two degreeoffreedom problem, and so can use the standard surfaceofsection methodto characterize the dynamics. Typical surfaces of section for a low energy trajectory (corresponding to the lowest quantumstate of this system, k = 2.0 andj = 1/2) are shownin Figures 9 and 10. The (Pp, p) section, Figure 9, showsstraightforward radial
1.00
1.27
1.55
1.82
2.10 RHO
2 37
2.BB
2.g2
3.20
~ Surface section a lowenergy of for trajectory ~a~ilto~i~ ~1,~thk = 2.0, for ~q.
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librational motionfor the most part, except for a prominenthigh order resonance visible as a chainof eight islands. The(I2, t#2) section, Figure10, shows relatively smallfluctuations of the phasearounda valueof $2 near n, together with a central resonant zonecorresponding the island chain in to Figure9. In the limit of large k andlowenergy,whichis the realmof"deep states" Withnegligible nonadiabatic coupling,the phase$2 has the constant valuen. Constancy ~b impliesperfect correlation between of 2 electronic and vibrational degrees of freedom.Nonadiabaticity is then manifest in the classical electron picture in deviations of ~2 from the value r~, such deviations correspondingto a loss of correlation betweenelectronic and nuclear variables. Examination nuclear configuration space projections of classical of analogJahnTellertrajectories providesadditional insight into the effects of nonadiabaticityon nuclear dynamics within this model.In Figures11 we show lowenergy two trajectories. Oneis obtained by solving the coupled equations of motion for hamiltonian Eq. 28; the other corresponds to motionat the sameenergyon the lower adiabatic potential surface [where the latter includes the BornHuang correction 1/8p2 (76, 105)]. Thetwo trajectories are remarkably similar! For motionon the lower, cylindrically symmetric adiabatic surface, the nuclear angular momentum a conserved is
2.60
2.74
2.87
3.01
3.15 PHI2
3.29
3.42
3.56
3.70
FigureI 0 (12, ~b2) surface of section at constant p for the trajectory of Figure
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0’g NONADIABATIC DYNAMICS 313
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quantity, whereasfor the low energy exact trajectory it is very nearly so. Increasing the energy reveals the effects of nonadiabaticity: In the slightly higher energy trajectory shownon the left in Figure 12, the nuclear radial turning points are beginning to develop a slight asymmetry,while on the right, at higher energy still, the projection of the nuclear motiondevelops loops and cusps, indicative of a nonadiabatic exchange of angular momentum with the electronic degrees of freedom. At very high energies, we obtain for someinitial conditions irregularlooking trajectories that can only be described as "chaotic." Wehave provided a brief overview of studies of nonadiabatic bound states using the classical electron model. There is clearly muchmoreto be learned about vibronic interactions using this approach. Particularly intriguing is the possibility of calculating boundstate energies or energy differences using somescmiclassical quantization of the classical analog hamiltonian, i.e. via a "requantization" of the original problem(221). Other Semiclassical Approaches
In the preceding subsection we stress the potential utility of the classical electron picture as a basis for a semiclassical description of nonadiabatic bound states. Another natural framework for such a theory is the multichannel generalization of the WKB method(222). Wetherefore briefly review somerecent progress in this direction. The general theory of multichannel WKB approaches to molecular scattering phenomena been reviewed by Eu (223). Hermanhas recently has investigated uniform multichannel semiclassical wavefunctions for nonadiabatic scattering, for both one (224) and multidimensional (225, 226) systems, and has also provided a helpful discussion and comparison of previous approaches to nonadiabatie scattering (225). Herman’sapproach seems particularly promising, and is complementary to the classical electron method discussed above. In the past few years some work has been done on the multichannel WKB quantization of vibronic bound states. Voronin et al (227) and O’Brien(228) have considered the high energy limit of the linear E x ~ JahnTeller problem,wherethe conical intersection represents a negligible perturbation of essentially harmonicmotion on either adiabatic surface. In this limit, good agreement is obtained (228) with the appropriate asymptotic energy level expressions of LonguetHiggins et al (79); in fact, impressive agreement with variational energy levels extends over a wide parameter range (227). At the other extreme, Karkach & Osherov have investigated the semiclassical quantization of deep states in a quadratic E x e JahnTeller system (100). In this case the nonadiabatic coupling terms were ignored, and a uniform quantization of the angular nuclear
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motion carried out after an adiabatic separation of the radial motion. A notable feature of this calculation is the imposition of nonperiodic boundary conditions on the semiclassical angular wavefunction, thus reflecting the requirement of a change of sign of the nuclear wavefunction upon traversing a loop in nuclear configuration space enclosing a conical intersection (72, 8085). The general problem of uniform quantization in multiwell potential with nonperiodic boundary conditions has recently been discussed in somedetail by Connoret al (229). A semiclassical theory for scattering resonances in the upper sheet of a twodimensional conical intersection has been developed by Osherov and coworkers (230, 231), and a semiclassical treatment of the absorption lineshape for an optical transition to a doublydegenerate electronic state is given in (232) (cf also 233). The multichannel WKB its generalization (or EBK)approach to bound states for general matrix hamiltonians has been discussed in the context of the Dirac electron (234) and quark dynamics (235).
ACKNOWLEDGMENTS We thank coworkers Kenneth IIaber and Josef Zwanziger for their
invaluable contributions to muchof the original research discussed in our account. This work was supported by grants from the National Science Foundation, the Petroleum Research Fund and the US Army Research Office. During the course of this writing, R.L.W. held a postdoctoral fellowship at the Corporate Research Science Laboratories, Exxon Research and Engineering Company.
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