Intramolecular Vibrational Redistribution Research Articles

Dissociative electron attachment to carbon tetrachloride probed by velocity map imaging.

Bond-breaking in CCl4via dissociative electron attachment (DEA) has been studied using a velocity map imaging (VMI) spectrometer. A number of effects related to the dissociation dynamics have been revealed. The near-zero eV s-wave electron attachment, which leads to the production of Cl- anions, is accompanied by a very efficient intramolecular vibrational redistribution. This is manifested by a small fraction of the excess energy being released in the form of the fragments' translation energy. A similar effect is observed for higher-lying electronic resonances with one exception: the resonance centered around 6.2 eV leads to the production of fast Cl2- fragments and their angular distribution is forward peaking. This behavior could not be explained with a single-electronic-state model in the axial recoil approximation and is most probably caused by bending dynamics initiated by a Jahn-Teller distortion of the transient anion. The CCl2- fragment has a reverse backward-peaking angular distribution, suggesting the presence of a long-distance electron hopping mechanism between the fragments.

Mid-infrared Laser Spectroscopy of Jet-Cooled Formic Acid Trimer: Mode-Dependent Line Broadening in the C-O Stretching Region.

Building on recent progress in the vibrational spectroscopy of the formic acid trimer, we present the first high-resolution measurements of the jet-cooled laser absorption spectrum of (HCOOH)3. The spectra of the lowest- and highest-frequency C-O stretching fundamentals are analyzed whereas the third band is not observed, complicated by monomer and dimer absorptions at 1219 cm-1 (8.2 μm). Vibration-rotation parameters are obtained for the band at 1172.31512(68) cm-1 whereas the C-O stretch at 1246.33(5) cm-1 exhibits a significantly larger breadth, allowing only resolution of the coarse PQR structure. Vibrational predissociation can be ruled out, and intramolecular vibrational redistribution mechanisms are discussed, particularly coupling to the concerted proton exchange within the cyclic dimer subunit. Ultimately, the question remains open. The prospects of high-resolution measurements of other trimer bands or isotope substitution experiments, which might assist in revealing the mode-specificity of the underlying broadening mechanisms, are discussed.

Photoinduced Dynamics of 13,13'-Diphenylpropyl-β-carotene.

Carotenoids are ubiquitous pigment systems in nature which are relevant to a range of processes, such as photosynthesis, but the detailed influence of substitutions at the polyene backbone on their photophysics is still underexplored. Here, we present a detailed experimental and theoretical investigation of the carotenoid 13,13'-diphenylpropyl-β-carotene using ultrafast transient absorption spectroscopy and steady-state absorption experiments in n-hexane and n-hexadecane, complemented by DFT/TDDFT calculations. In spite of their bulkiness and their potential capability to "fold back" onto the polyene system, which could result in π-stacking effects, the phenylpropyl residues have only a minor impact on the photophysical properties compared with the parent compound β-carotene. Ultrafast spectroscopy finds lifetimes of 200-300 fs for the S2 state and 8.3-9.5 ps for the S1 state. Intramolecular vibrational redistribution with time constants in the range 0.6-1.4 ps is observed in terms of a spectral narrowing of the S1 spectrum over time. We also find clear indications of the presence of vibrationally hot molecules in the ground electronic state (S0*). The DFT/TDDFT calculations confirm that the propyl spacer electronically decouples the phenyl and polyene π-systems and that the substituents in the 13 and 13' positions point away from the polyene system.

Cascade Infrared Thermal Photon Emission

The later stages of cooling of molecules and clusters in the interstellar medium are dominated by emission of vibrational infrared radiation. With the development of cryogenic storage it has become possible to experimentally study these processes. Recent storage ring results demonstrate that intramolecular vibrational redistribution takes place within the cooling process, and an harmonic cascade model has been used to interpret the data. Here we analyze this model and show that the energy distributions and the photon emission rates develop into near-universal functions that can be characterized with only a few parameters, irrespective of the precise vibrational spectra and oscillator strengths of the systems. We show that the photon emission rate and emitted power vary linearly with total excitation energy with a small offset. The time developments of ensemble internal energy distributions are calculated with respect to their first two moments. The excitation energy decreases exponentially with a rate constant which is the average of all k1→0 Einstein coefficients, and the time development of the variance is also calculated.

Electron Energy Loss Processes in Methyl Methacrylate: Excitation and Bond Breaking.

Details of electron-induced chemistry of methyl methacrylate (MMA) upon complexation are revealed by combining gas-phase 2D electron energy loss spectroscopy with electron attachment spectroscopy of isolated MMA and its clusters. We show that even though isolated MMA does not form stable parent anions, it efficiently thermalizes the incident electrons via intramolecular vibrational redistribution, leading to autodetachment of slow electrons. This autodetachment channel is reduced in clusters due to intermolecular energy transfer and stabilization of parent molecular anions. Bond breaking via dissociative electron attachment leads to an extensive range of anion products. The dominant OCH3- channel is accessible via core-excited resonances with threshold above 5 eV, despite the estimated thermodynamic threshold below 3 eV. This changes in clusters, where MnOCH3- anions are observed in a lower-lying resonance due to neutral dissociation of the 1(n, π*) state and electron self-scavenging. The present findings have implications for electron-induced chemistry in lithography with poly(methyl methacrylate).

Femtosecond Time-Resolved Observation of Relaxation and Wave Packet Dynamics of the S1 State in Electronically Excited o-Fluoroaniline

Quantum beat frequency is the basis for understanding interference effects and vibrational wave packet dynamics and has important applications. Using femtosecond time-resolved mass spectrometry and femtosecond time-resolved photoelectron image combined with theoretical calculations, we study the electronic excited-state relaxation of o-fluoraniline molecule and the time-dependent evolution of vibrational wave packets between different eigenstates. After the molecule absorbs a photon of 288.3 nm and is excited to the S1 state, intramolecular vibrational redistribution first occurs on the time scale τ1 = 349 fs, and then the transition to the triplet state occurs through the intersystem crossing on the time scale τ2 = 583 ps, and finally, the triplet state occurs decays slowly through the time scale τ3 = 2074 ps. We find the intramolecular vibrational redistribution is caused by the 00, 10b1 and 16a1 vibrational modes of the Sl state origin. That is, the 288.3 nm femtosecond laser excites the molecule to the S1 state, and the continuous flow of the vibrational wave packet prepares a coherent superposition state of three vibrational modes. Through extracting the oscillation of different peak intensities in the photoelectron spectrum, we observe reversible changes caused by mutual interference of the S1 00, S1 10b1 and S1 16a1 states when the wave packets flow. When the pump pulse is 280 nm, the beat frequency disappears completely. This is explained in terms of increases in the vibrational field density and characteristic period of oscillation, and statistical averaging makes the quantum effect smooth and indistinguishable. In addition, the Rydberg component of the S1 state is more clearly resolved by combining experiment and theory.

Vibrational relaxation by methylated xanthines in solution: Insights from 2D IR spectroscopy and calculations.

Two-dimensional infrared (2D IR) spectroscopy, infrared pump-infrared probe spectroscopy, and density functional theory calculations were used to study vibrational relaxation by ring and carbonyl stretching modes in a series of methylated xanthine derivatives in acetonitrile and deuterium oxide (heavy water). Isotropic signals from the excited symmetric and asymmetric carbonyl stretch modes decay biexponentially in both solvents. Coherent energy transfer between the symmetric and asymmetric carbonyl stretching modes gives rise to a quantum beat in the time-dependent anisotropy signals. The damping time of the coherent oscillation agrees with the fast decay component of the carbonyl bleach recovery signals, indicating that this time constant reflects intramolecular vibrational redistribution (IVR) to other solute modes. Despite their similar frequencies, the excited ring modes decay monoexponentially with a time constant that matches the slow decay component of the carbonyl modes. The slow decay times, which are faster in heavy water than in acetonitrile, approximately match the ones observed in previous UV pump-IR probe measurements on the same compounds. The slow component is assigned to intermolecular energy transfer to solvent bath modes from low-frequency solute modes, which are populated by IVR and are anharmonically coupled to the carbonyl and ring stretch modes. 2D IR measurements indicate that the carbonyl stretching modes are weakly coupled to the delocalized ring modes, resulting in slow exchange that cannot explain the common solvent-dependence. IVR is suggested to occur at different rates for the carbonyl vs ring modes due to differences in mode-specific couplings and not to differences in the density of accessible states.

Generalized Resonance Energy Transfer Theory: Applications to Vibrational Energy Flow in Optical Cavities.

A general rate theory for resonance energy transfer (gRET) is formulated to incorporate any degrees of freedom (e.g., rotation, vibration, exciton, and polariton) as well as coherently coupled composite donor or acceptor states. The compact rate expression allows us to establish useful relationships: (i) detailed balance condition when the donor and acceptor are at the same temperature; (ii) proportionality to the product of dipole correlation tensors, which is not necessarily equivalent to spectral overlap; (iii) scaling with the effective coherent size, i.e., the number of coherently coupled molecules or modes; (iv) decomposition of collective rate in homogeneous systems into the monomer and coherence contributions such that the ratio of the two defines the quantum enhancement factor F; (v) spatial and orientational dependences as derived from the interaction potential. For the special case of exciton transfer, the general rate formalism reduces to FRET or its multichromophoric extension. When applied to cavity-assisted vibrational energy transfer between molecules or within a molecule, the general rate expression provides an intuitive explanation of intriguing phenomena such as cooperativity, resonance, and nonlinearity in the collective vibrational strong coupling (VSC) regime, as demonstrated in recent simulations. The relevance of gRET to cavity-catalyzed reactions and intramolecular vibrational redistribution is discussed and will lead to further theoretical developments.

Thermionic Emission of Negative Ions of Molecules and Small Clusters as a Probe of Low-Energy Attachment.

We have been studying the thermionic emission of negatively charged molecules and small clusters for more than a decade. The kinetic energy released distribution (KERD) of mass-selected negative ions has been measured with a velocity map imaging spectrometer. A comparison of the experimental KERD to detailed balance models provided information on the reverse process, namely, the electron attachment to the parent. The electron attachment to neutral systems (reverse process of the electron emission from anions) is usually described in a simplified way as a single electron capture in the framework of the classical Langevin model. Our measurements show that this approach is insufficient and that, in addition to the capture step, an intramolecular vibrational redistribution (IVR) step should be included. As far as multiply charged anions are concerned, the electron attachment to anions (reverse process of the electron emission from dianions) is strongly affected by the repulsive Coulomb barrier (RCB). Previous studies assumed a pure over-the-barrier process, which is in disagreement with our study. Indeed, electron emission is measured below the RCB, revealing significant thermal tunneling. In the present review, we summarize these works on singly and doubly charged anions in an attempt to present a unified view of the involved processes. It is worth noting that the detailed measurements of KERDs in the very low kinetic energy region (typically around 0.1 eV) have been made possible thanks to electron imaging methods, without which all of this work could never have been done, with time-resolution capabilities allowing the disentangling of direct and delayed electron emission.

Excitation relaxation dynamics of carotenoids constituting the diadinoxanthin cycle.

Carotenoids (Cars) exhibit two functions in photosynthesis, light-harvesting and photoprotective functions, which are performed through the excited states of Cars. Therefore, increasing our knowledge on excitation relaxation dynamics of Cars is important for understanding of the functions of Cars. In light-harvesting complexes, there exist Cars functioning by converting the π-conjugation number in response to light conditions. It is well known that some microalgae have a mechanism controlling the conjugation number of Cars, called as the diadinoxanthin cycle; diadinoxanthin (10 conjugations) is accumulated under low light, whereas diatoxanthin (11 conjugations) appears under high light. However, the excitation relaxation dynamics of these two Cars have not been clarified. In the present study, we investigated excitation relaxation dynamics of diadinoxanthin and diatoxanthin in relation to their functions, by the ultrafast fluorescence spectroscopy. After an excitation to the S2 state, the intramolecular vibrational redistribution occurs, followed by the internal conversion to the S1 state. The S2 lifetimes were analyzed to be 175fs, 155fs, and 140fs in diethyl ether, ethanol, and acetone, respectively, for diadinoxanthin, and 155fs, 135fs, and 125fs in diethyl ether, ethanol, and acetone, respectively for diatoxanthin. By converting diadinoxanthin to diatoxanthin, the absorption spectra shift to longer wavelengths by 5-7nm, and lifetimes of S2 and S1 states decrease by 11-13% and 52%, respectively. Differences in levels and lifetimes of excited states between diadinoxanthin and diatoxanthin are small; therefore, it is suggested that changes in the energy level of chlorophyll a are necessary to efficiently control the functions of the diadinoxanthin cycle.

Intramolecular vibrational redistribution in formic acid and its deuterated forms.

The intramolecular vibrational relaxation dynamics of formic acid and its deuterated isotopologues is simulated on the full-dimensional potential energy surface of Richter and Carbonnière [J. Chem. Phys. 148, 064303 (2018)] using the Heidelberg MCTDH package. We focus on couplings with the torsion vibrational modes close to the trans-cis isomerization coordinate from the dynamics of artificially excited vibrational mode overtones. The bright C-O stretch vibrational mode is coupled to the out-of-the plane torsion mode in HCOOH, where this coupling could be exploited for laser-induced trans-to-cis isomerization. Strong isotopic effects are observed: deuteration of the hydroxyl group, i.e., in HCOOD and DCOOD, destroys the C-O stretch to torsion mode coupling whereas in DCOOH, little to no effect is observed.

Driving chemical reactions with polariton condensates

When molecular transitions strongly couple to photon modes, they form hybrid light-matter modes called polaritons. Collective vibrational strong coupling is a promising avenue for control of chemistry, but this can be deterred by the large number of quasi-degenerate dark modes. The macroscopic occupation of a single polariton mode by excitations, as observed in Bose-Einstein condensation, offers promise for overcoming this issue. Here we theoretically investigate the effect of vibrational polariton condensation on the kinetics of electron transfer processes. Compared with excitation with infrared laser sources, the vibrational polariton condensate changes the reaction yield significantly at room temperature due to additional channels with reduced activation barriers resulting from the large accumulation of energy in the lower polariton, and the many modes available for energy redistribution during the reaction. Our results offer tantalizing opportunities to use condensates for driving chemical reactions, kinetically bypassing usual constraints of fast intramolecular vibrational redistribution in condensed phase.

Compression Behavior and Vibrational Properties of New Energetic Material LLM-105 Analyzed Using the Dispersion-Corrected Density Functional Theory.

The 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) is a newly energetic material with an excellent performance and low sensitivity and has attracted considerable attention. On the basis of the dispersion-corrected density functional theory (DFT-D), the high-pressure responses of vibrational properties, in conjunction with structural properties, are used to understand its intermolecular interactions and anisotropic properties under hydrostatic and uniaxial compressions. At ambient and pressure conditions, the DFT-D scheme could reasonably describe the structural parameters of LLM-105. The hydrogen bond network, resembling a parallelogram shape, links two adjacent molecules and contributes to the structure stability under hydrostatic compression. The anisotropy of LLM-105 is pronounced, especially for Raman spectra under uniaxial compression. Specifically, the red-shifts of modes are obtained for [100] and [010] compressions, which are caused by the pressure-induced enhance of the strength of the hydrogen bonds. Importantly, coupling modes and discontinuous Raman shifts are observed along [010] and [001] compressions, which are related to the intramolecular vibrational redistribution and possible structural transformations under uniaxial compressions. Overall, the detailed knowledge of the high-pressure responses of LLM-105 is established from the atomistic level. Uniaxial compression responses provide useful insights for realistic shock conditions.

Quasiclassical Direct Dynamics Trajectory Simulations of Organometallic Reactions.

Homogeneous metal-mediated organometallic reactions represent a very large and diverse reaction class. Density functional theory calculations are now routinely carried out and reported for analyzing organometallic mechanisms and reaction pathways. While density functional theory calculations are extremely powerful to understand the energy and structure of organometallic reactions, there are several assumptions in their use and interpretation to define reaction mechanisms and to analyze reaction selectivity. Almost always it is assumed that potential energy structures calculated with density functional theory adequately describe mechanisms and selectivity within the framework of statistical theories, for example, transition state theory and RRKM theory. However, these static structures and corresponding energy landscapes do not provide atomic motion information during reactions that could reveal nonstatistical intermediates without complete intramolecular vibrational redistribution and nonintrinsic reaction coordinate (non-IRC) pathways. While nonstatistical intermediates and non-IRC reaction pathways are now relatively well established for organic reactions, these dynamic effects have heretofore been highly underexplored in organometallic reactions. Through a series of quasiclassical density functional theory direct dynamics trajectory studies, my group has recently demonstrated that dynamic effects occur in a variety of fundamental organometallic reactions, especially bond activation reactions. For example, in the C-H activation reaction between methane and [Cp*(PMe3)IrIII(CH3)]+, while the density functional theory energy landscape showed a two-step oxidative cleavage and reductive coupling mechanism, trajectories revealed a mixture of this two-step mechanism and a dynamic one-step mechanism that skipped the [Cp*(PMe3)IrV(H)(CH3)2]+ intermediate. This study also showed that despite a methane σ-complex being located on the density functional theory surface before oxidative cleavage and after reductive coupling, this intermediate is always skipped and should not be considered an intermediate during reactive trajectories. For non-IRC reaction pathways, quasiclassical direct dynamics trajectories showed that for the isomerization of [Tp(NO)(PMe3)W(η2-benzene)] to [Tp(NO)(PMe3)W(H)(Ph)], there are many dynamic reaction pathway connections due to a relatively flat energy landscape and π coordination is not necessary for C-H bond activation through oxidative cleavage. Trajectories also showed that dynamic effects are important in selectivity for ethylene C-H activation versus π coordination in reaction with Cp(PMe3)2Re, and trajectories provide a more quantitative model of selectivity than transition state theory. Quasiclassical trajectories examining Au-catalyzed monoallylic diol cyclizations showed dynamic coupling of several reaction steps that include alkoxylation π bond addition, proton shuttling, and water elimination reaction steps. Overall, these studies highlight the need to use direct dynamics trajectory simulations to consider atomic motion during reactions to understand organometallic reaction mechanisms and selectivity.

Observation of a dipole-bound excited state in 4-ethynylphenoxide and comparison with the quadrupole-bound excited state in the isoelectronic 4-cyanophenoxide.

Negative ions do not possess Rydberg states but can have Rydberg-like nonvalence excited states near the electron detachment threshold, including dipole-bound states (DBSs) and quadrupole-bound states (QBSs). While DBSs have been studied extensively, quadrupole-bound excited states have been more rarely observed. 4-cyanophenoxide (4CP-) was the first anion observed to possess a quadrupole-bound exited state 20cm-1 below its detachment threshold. Here, we report the observation of a DBS in the isoelectronic 4-ethynylphenoxide anion (4EP-), providing a rare opportunity to compare the behaviors of a dipole-bound and a quadrupole-bound excited state in a pair of very similar anions. Photodetachment spectroscopy (PDS) of cryogenically cooled 4EP- reveals a DBS 76cm-1 below its detachment threshold. Photoelectron spectroscopy (PES) at 266nm shows that the electronic structure of 4EP- and 4CP- is nearly identical. The observed vibrational features in both the PDS and PES, as well as autodetachment from the nonvalence excited states, are also found to be similar for both anions. However, resonant two-photon detachment (R2PD) from the bound vibrational ground state is observed to be very different for the DBS in 4EP- and the QBS in 4CP-. The R2PD spectra reveal that decays take place from both the DBS and QBS to the respective anion ground electronic states within the 5ns detachment laser pulse due to internal conversion followed by intramolecular vibrational redistribution and relaxation, but the decay mechanisms appear to be very different. In the R2PD spectrum of 4EP-, we observe strong threshold electron signals, which are due to detachment, by the second photon, of highly rotationally excited anions resulted from the decay of the DBS. On the other hand, in the R2PD spectrum of 4CP-, we observe well-resolved vibrational peaks due to the three lowest-frequency vibrational modes of 4CP-, which are populated from the decay of the QBS. The different behaviors of the R2PD spectra suggest unexpected differences between the relaxation mechanisms of the dipole-bound and quadrupole-bound excited states.

Vibrational mode-specificity in the dynamics of the Cl + C2H6 → HCl + C2H5 reaction.

We report a detailed dynamics study on the mode-specificity of the Cl + C2H6 → HCl + C2H5 H-abstraction reaction. We perform quasi-classical trajectory simulations using a recently developed high-level ab initio full-dimensional potential energy surface by exciting five different vibrational modes of ethane at four collision energies. We find that all the studied vibrational excitations, except that of the CC-stretching mode, clearly promote the title reaction, and the vibrational enhancements are consistent with the predictions of the Sudden Vector Projection (SVP) model, with the largest effect caused by the CH-stretching excitations. Intramolecular vibrational redistribution is also monitored for the differently excited ethane molecule. Our results indicate that the mechanism of the reaction changes with increasing collision energy, with no mode-specificity at high energies. The initial translational energy mostly converts into product recoil, while a significant part of the excess vibrational energy remains in the ethyl radical. An interesting competition between translational and vibrational energies is observed for the HCl vibrational distribution: the effect of exciting the low-frequency ethane modes, having small SVP values, is suppressed by translational excitation, whereas a part of the excess vibrational energy pumped into the CH-stretching modes (larger SVP values) efficiently flows into the HCl vibration.

Spectroscopy and Infrared Photofragmentation Dynamics of Mixed Ligand Ion-Molecule Complexes: Au(CO)x(N2O)y.

We report a combined experimental and computational study of the structure and fragmentation dynamics of mixed ligand gas-phase ion-molecule complexes. Specifically, we have studied the infrared spectroscopy and vibrationally induced photofragmentation dynamics of mass-selected Au(CO)x(N2O)y+ complexes. The structures can be understood on the basis of local CO and N2O chromophores in different solvation shells with CO found preferentially in the core. Rich fragmentation dynamics are observed as a function of complex composition and the vibrational mode excited. The dynamics are characterized in terms of branching ratios for different ligand loss channels in light of calculated internal energy distributions. Intramolecular vibrational redistribution appears to be rapid, and dissociation is observed into all energetically accessible channels with little or no evidence for preferential breaking of the weakest intermolecular interactions.

An enhanced sampling QM/AMOEBA approach: The case of the excited state intramolecular proton transfer in solvated 3-hydroxyflavone.

We present an extension of the polarizable quantum mechanical (QM)/AMOEBA approach to enhanced sampling techniques. This is achieved by connecting the enhanced sampling PLUMED library to the machinery based on the interface of Gaussian and Tinker to perform QM/AMOEBA molecular dynamics. As an application, we study the excited state intramolecular proton transfer of 3-hydroxyflavone in two solvents: methanol and methylcyclohexane. By using a combination of molecular dynamics and umbrella sampling, we find an ultrafast component of the transfer, which is common to the two solvents, and a much slower component, which is active in the protic solvent only. The mechanisms of the two components are explained in terms of intramolecular vibrational redistribution and intermolecular hydrogen-bonding, respectively. Ground and excited state free energies along an effective reaction coordinate are finally obtained allowing for a detailed analysis of the solvent mediated mechanism.

Direct comparison of amplitude and geometric measures of spectral inhomogeneity using phase-cycled 2D-IR spectroscopy.

Two-dimensional infrared (2D-IR) spectroscopy provides access to equilibrium dynamics with the extraction of the frequency-fluctuation correlation function (FFCF) from the measured spectra. Several different methods of obtaining the FFCF from experimental spectra, such as the center line slope (CLS), ellipticity, phase slope, and nodal line slope, all depend on the geometrical nature of the 2D line shape and necessarily require spectral extent in order to achieve a measure of the FFCF. Amplitude measures, on the other hand, such as the inhomogeneity index, rely only on signal amplitudes and can, in principle, be computed using just a single point in a 2D spectrum. With a pulse shaper-based 2D-IR spectrometer, in conjunction with phase cycling, we separate the rephasing and nonrephasing signals used to determine the inhomogeneity index. The same measured data provide the absorptive spectrum, needed for the CLS. Both methods are applied to two model molecular systems: tungsten hexacarbonyl (WCO6) and methylcyclopentadienyl manganese tricarbonyl [Cp'Mn(CO)3, MCMT]. The three degenerate IR modes of W(CO)6 lack coherent modulation or noticeable intramolecular vibrational redistribution (IVR) and are used to establish a baseline comparison. The two bands of the MCMT tripod complex include intraband coherences and IVR as well as likely internal torsional motion on a few-picosecond time scale. We find essentially identical spectral diffusion, but faster, non-equilibrium dynamics lead to differences in the FFCFs extracted with the two methods. The inhomogeneity index offers an advantage in cases where spectra are complex and energy transfer can mimic line shape changes due to frequency fluctuations.

A phase diagram for energy flow-limited reactivity.

Intramolecular energy flow (also known as intramolecular vibrational redistribution or IVR) is often assumed in Rice-Ramsperger-Kassel-Marcus, transition state, collisional energy transfer, and other rate calculations not to be an impediment to reaction. In contrast, experimental spectroscopy, computational results, and models based on Anderson localization have shown that ergodicity is achieved rather slowly during molecular energy flow. The statistical assumption in rate theories might easily fail due to quantum localization. Here, we develop a simple model for the interplay of IVR and energy transfer and simulate the model with near-exact quantum dynamics for a 10-degree of freedom system composed of two five-mode molecular fragments. The calculations are facilitated by applying the van Vleck transformation to local random matrix models of the vibrational Hamiltonian. We find that there is a rather sharp "phase transition" as a function of molecular anharmonicity "a" between a region of facile energy transfer and a region limited by IVR and incomplete accessibility of the state space (classically, the phase space). The very narrow transition range of the order parameter a happens to lie right in the middle of the range expected for molecular torsion, bending, and stretching vibrations, thus demonstrating that reactive energy transfer dynamics several kBT above the thermal energy occurs not far from the localization boundary, with implications for controllability of reactions.