Intermolecular Vibrational Energy Transfer Research Articles

Molecular Vibrational Polariton Dynamics: What Can Polaritons Do?

ConspectusWhen molecular vibrational modes strongly couple to virtual states of photonic modes, new molecular vibrational polariton states are formed, along with a large population of dark reservoir modes. The polaritons are much like the bonding and antibonding molecular orbitals when atomic orbitals form molecular bonds, while the dark modes are like nonbonding orbitals. Because the polariton states are half-matter and half-light, whose energy is shifted from the parental states, polaritons are predicted to modify chemistry under thermally activated conditions, leading to an exciting and emerging field known as polariton chemistry that could potentially shift paradigms in chemistry. Despite several published results supporting this concept, the chemical physics and mechanism of polariton chemistry remain elusive. One reason for this challenge is that previous works cannot differentiate polaritons from dark modes. This limitation makes delineating the contributions to chemistry from polaritons and dark states difficult. However, this level of insight is critical for developing a solid mechanism for polariton chemistry to design and predict the outcome of strong coupling with any given reaction. My group addressed the challenge of differentiating the dynamics of polaritons and dark modes by ultrafast two-dimensional infrared (2D IR) spectroscopy. Specifically, (1) we found that polaritons can facilitate intra- and intermolecular vibrational energy transfer, opening a pathway to control vibrational energy flow in liquid-phase molecular systems, and (2) by studying a single-step isomerization event, we verified that indeed polaritons can modify chemical dynamics under strong coupling conditions, but in contrast, the dark modes behave like uncoupled molecules and do not change the dynamics. This finding confirmed the central concept of polariton chemistry: polaritons modify the potential energy landscape of reactions. The result also clarified the role of dark modes, which lays a critical foundation for designing cavities for future polariton chemistry. Aside from using 2D IR spectroscopy to study polariton chemistry, we also used the same technique to develop molecular polaritons into a potential quantum simulation platform. We demonstrated that polaritons have Rabi oscillations, and using a checkerboard cavity design, we showed that polaritons could have large nonlinearity across space. We further used the checkerboard polaritons to simulate coherence transfer and visualize it. A unidirectional coherence transfer was observed, indicating non-Hermitian dynamics. The highlighted efforts in this Account provide a solid understanding of the capability of polaritons for chemistry and quantum information science. I conclude this Account by discussing a few challenges for moving polariton chemistry toward being predictable and making the polariton quantum platform a complement to existing systems.

Polarization effects on intermolecular vibrational energy transfer analyzed by 2DIR spectroscopy

AbstractIn the present work, we analyze the influence of the polarization effects taking place during the course of a 2DIR spectroscopy experiment performed on a molecular system undergoing an intermolecular vibrational energy transfer process. When both donor and acceptor molecules participating in the vibrational energy transfer are embedded in a host solvent, they face rotational diffusion that strongly distorts the resulting 2DIR spectra. It could be expected that the difference between rotational diffusion constants will be of particular interest. For this purpose, the polarization effects are discussed according to the different orderings of the laser‐molecule interactions. Next, we study the distortions of the spectra as a function of the rotational diffusion constants of the individual molecules. The knowledge of these polarization effects is relevant to the interpretation of the spectra. Finally, the conclusions reached in this work for a vibrational energy transfer are valid for any other type of third‐order optical process performed on the same molecular system.

Intermolecular vibrational energy transfer between SWCNTs with different chiralities

Ultrafast spectroscopy was performed for two kinds of SWCNT samples; a sample purified to have a single chirality (purified) and one containing variety of chiralities (non-purified). There are three relaxation processes with corresponding rates which were estimated as 10ps-1,2ps-1,and0.5ps-1. The fastest rate is attributed to intraband relaxation in the electronic excited state, and the other two are for parallel relaxation process of interband relaxation to the electronic ground state. Vibrational frequency of radial breathing mode was found to show up-shift only in the non-purified sample (not in the purified one), which indicates intermolecular vibrational energy transfer between SWCNTs with different chiralities from each other.

Intramolecular vibrational energy redistribution in nucleobases: Excitation of NH stretching vibrations in adenine-uracil + H2O.

Redistribution of vibrational energy in the adenine-uracil base pair is studied when the base pair undergoes an intermolecular interaction with an overtone-bending vibration excited H2O(2νbend) molecule. Energy transfer is calculated using the structural information obtained from density functional theory in the solution of the equations of motion. Intermolecular vibrational energy transfer (VET) from H2O(2νbend) to the uracil-NH stretching mode is efficient and rapidly followed by intramolecular vibrational energy redistribution (IVR) resulting from coupling between vibrational modes. An important pathway is IVR carrying energy to the NH-stretching mode of the adenine moiety in a subpicosecond scale, the energy build-up being sigmoidal, when H2O interacts with the uracil-NH bond. The majority of intermolecular hydrogen bonds between the base pair and H2O are weakened but unbroken during the ultrafast energy redistribution period. Lifetimes of intermolecular HB are on the order of 0.5ps. The efficiency of IVR in the base pair is due to near-resonance between coupled CC and CN vibrations. The resonance also exists between the frequencies of H2O bend and NH stretch, thus facilitating VET. When H2O interacts with the NH bond at the adenine end of the base pair, energy flow in the reverse direction to the uracil-NH stretch is negligible, the unidirectionality discussed in terms of the effects of uracil CH stretches. The energy distributed in the CH bonds is found to be significant. The IVR process is found to be nearly temperature independent between 200 and 400K.

Intermolecular Vibration Energy Transfer Process in Two CL-20-Based Cocrystals Theoretically Revealed by Two-Dimensional Infrared Spectra.

Inspired by the recent cocrystallization and theory of energetic materials, we theoretically investigated the intermolecular vibrational energy transfer process and the non-covalent intermolecular interactions between explosive compounds. The intermolecular interactions between 2,4,6-trinitrotoluene (TNT) and 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) and between 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) and CL-20 were studied using calculated two-dimensional infrared (2D IR) spectra and the independent gradient model based on the Hirshfeld partition (IGMH) method, respectively. Based on the comparison of the theoretical infrared spectra and optimized geometries with experimental results, the theoretical models can effectively reproduce the experimental geometries. By analyzing cross-peaks in the 2D IR spectra of TNT/CL-20, the intermolecular vibrational energy transfer process between TNT and CL-20 was calculated, and the conclusion was made that the vibrational energy transfer process between CL-20 and TNTII (TNTIII) is relatively slower than between CL-20 and TNTI. As the vibration energy transfer is the bridge of the intermolecular interactions, the weak intermolecular interactions were visualized using the IGMH method, and the results demonstrate that the intermolecular non-covalent interactions of TNT/CL-20 include van der Waals (vdW) interactions and hydrogen bonds, while the intermolecular non-covalent interactions of HMX/CL-20 are mainly comprised of vdW interactions. Further, we determined that the intermolecular interaction can stabilize the trigger bond in TNT/CL-20 and HMX/CL-20 based on Mayer bond order density, and stronger intermolecular interactions generally indicate lower impact sensitivity of energetic materials. We believe that the results obtained in this work are important for a better understanding of the cocrystal mechanism and its application in the field of energetic materials.

Vibrational dynamics of iron pentacarbonyl in cryogenic matrices.

Iron pentacarbonyl is a textbook example of fluxionality. We trap the molecule in cryogenic matrices to study the vibrational dynamics of CO stretching modes involved in the fluxional rearrangement. The infrared spectrum in Ar and N2 is composed of about ten narrow bands in the spectral range of interest, indicating the population of various lattice sites and a lowering of the molecular symmetry in the trapping sites. The vibrational dynamics is explored by means of infrared stimulated photon echoes at the femtosecond scale. Vibrational dephasing and population relaxation times are obtained. The non-linear signals exhibit strong oscillations useful to disentangle the site composition of the absorption spectrum. The population relaxation involves at least two characteristic times. An evolution of the photon echo signals with the waiting time is observed. The behavior of all the signals can be reproduced within a simple model that describes the population relaxation occurring in two steps: relaxation of v = 1 (population time T1 < 100ps) and return to v = 0 (recovery time > 1ns). These two steps explain the evolution of the oscillations with the waiting time in the photon echo signals. These results discard fluxional rearrangement on the time scale of hundreds of ps in our samples. Dephasing times are of the same order of magnitude as T1: dephasing processes due to the matrix environment are rather inefficient. The photon echo experiments also reveal that intermolecular resonant vibrational energy transfers between guest molecules occur at the hundreds of ps time scale in concentrated samples (guest/host > 104).

Molecular vibrational polariton: Its dynamics and potentials in novel chemistry and quantum technology.

Molecular vibrational polaritons, a hybridized quasiparticle formed by the strong coupling between molecular vibrational modes and photon cavity modes, have attracted tremendous attention in the chemical physics community due to their peculiar influence on chemical reactions. At the same time, the half-photon half-matter characteristics of polaritons make them suitable to possess properties from both sides and lead to new features that are useful for photonic and quantum technology applications. To eventually use polaritons for chemical and quantum applications, it is critical to understand their dynamics. Due to the intrinsic time scale of cavity modes and molecular vibrational modes in condensed phases, polaritons can experience dynamics on ultrafast time scales, e.g., relaxation from polaritons to dark modes. Thus, ultrafast vibrational spectroscopy becomes an ideal tool to investigate such dynamics. In this Perspective, we give an overview of recent ultrafast spectroscopic works by our group and others in the field. These recent works show that molecular vibrational polaritons can have distinct dynamics from its pure molecular counterparts, such as intermolecular vibrational energy transfer and hot vibrational dynamics. We then discuss some current challenges and future opportunities, such as the possible use of ultrafast vibrational dynamics, to understand cavity-modified reactions and routes to develop molecular vibrational polaritons as new room temperature quantum platforms.

Collective Vibrational Strong Coupling Effects on Molecular Vibrational Relaxation and Energy Transfer: Numerical Insights via Cavity Molecular Dynamics Simulations**

AbstractFor a small fraction of hot CO2 molecules immersed in a liquid‐phase CO2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO2 molecules and a cavity mode accelerates hot‐molecule relaxation. This acceleration stems from the fact that polaritons can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates 1) resonantly depend on the cavity mode detuning, 2) cooperatively depend on Rabi splitting, and 3) collectively scale with the number of hot molecules. For larger cavity volumes, the average VSC effect per molecule can remain meaningful for up to N≈104 molecules forming VSC. Moreover, the transiently excited lower polariton prefers to relax by transferring its energy to the tail of the molecular energy distribution rather than distributing it equally to all thermal molecules. As far as the parameter dependence is concerned, the vibrational relaxation data presented here appear analogous to VSC catalysis in Fabry–Pérot microcavities.

Collective Vibrational Strong Coupling Effects on Molecular Vibrational Relaxation and Energy Transfer: Numerical Insights via Cavity Molecular Dynamics Simulations*.

For a small fraction of hot CO2 molecules immersed in a liquid-phase CO2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO2 molecules and a cavity mode accelerates hot-molecule relaxation. This acceleration stems from the fact that polaritons can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates 1) resonantly depend on the cavity mode detuning, 2) cooperatively depend on Rabi splitting, and 3) collectively scale with the number of hot molecules. For larger cavity volumes, the average VSC effect per molecule can remain meaningful for up to N≈104 molecules forming VSC. Moreover, the transiently excited lower polariton prefers to relax by transferring its energy to the tail of the molecular energy distribution rather than distributing it equally to all thermal molecules. As far as the parameter dependence is concerned, the vibrational relaxation data presented here appear analogous to VSC catalysis in Fabry-Pérot microcavities.

Understanding radiative transitions and relaxation pathways in plexcitons

Summary Molecular aggregates on plasmonic nanoparticles have emerged as attractive systems for the studies of polaritonic light-matter states, called plexcitons. Such systems are tunable, scalable, easy to synthesize, and offer sub-wavelength confinement, all while giving access to the ultrastrong light-matter coupling regime, promising a plethora of applications. However, the complexity of these materials prevented the understanding of their excitation and relaxation phenomena. Here, we follow the relaxation pathways in plexcitons and conclude that while the metal destroys the optical coherence, the molecular aggregate coupled to surface processes significantly contributes to the energy dissipation. We use two-dimensional electronic spectroscopy with theoretical modeling to assign the different relaxation processes to either molecules or metal nanoparticle. We show that the dynamics beyond a few femtoseconds has to be considered in the language of hot electron distributions instead of the accepted lower and upper polariton branches and establish the framework for further understanding.

Intermolecular vibrational energy transfer enabled by microcavity strong light-matter coupling.

Selective vibrational energy transfer between molecules in the liquid phase, a difficult process hampered by weak intermolecular forces, is achieved through polaritons formed by strong coupling between cavity photon modes and donor and acceptor molecules. Using pump-probe and two-dimensional infrared spectroscopy, we found that the excitation of the upper polariton, which is composed mostly of donors, can efficiently relax to the acceptors within ~5 picoseconds. The energy-transfer efficiency can be further enhanced by increasing the cavity lifetime, suggesting that the energy transfer is a polaritonic process. This vibrational energy-transfer pathway opens doors for applications in remote chemistry, sensing mechanisms, and vibrational polariton condensation.

Ultrafast Intermolecular Vibrational Energy Transfer in Hexahydro-1,3,5-trinitro-1,3,5-triazine in Molecular Crystal by 2D IR Spectroscopy

Cyclic nitramine hexahydro-1,3,5-trinitro-s-triazine (HHTT) is an important energetic molecule with a variety of applications. In this work, structural dynamics and vibrational-energy transfer dynamics of HHTT were investigated using steady-state infrared (IR), femtosecond time-resolved IR, and two-dimensional (2D) IR spectroscopic methods. Two different structural forms of HHTT (isolated molecules dissolved in DMSO and microcrystal dispersed in paraffin oil) were examined using the NO2 asymmetric stretching mode as a structural marker. Both intra- and intermolecular vibrational energy transfers were observed in HHTT microcrystal, where the well-known α-conformation was retained. However, less perfect α-HHTT species was found in DMSO. An intermolecular energy dissipation pathway was found to be related to Davydov splitting in the microcrystal form of HHTT, which originates from intermolecular interactions (e.g., electrostatic and hydrogen bonds). Experimental results were supported by quantum-chemistry computations. In addition, both vibrational excited-state relaxation and vibrational energy-transfer processes were found to be more efficient in HHTT microcrystal than in the solvated form. Our work provides a chemical-bond level of insight into the nitro group-containing energetic materials.

Ultrafast Vibrational Energy Transfer through the Covalent Bond and Intra- and Intermolecular Hydrogen Bonds in a Supramolecular Dimer by Two-Dimensional Infrared Spectroscopy.

In this work, the structural fluctuations and vibrational energy transfer dynamics in a supramolecular homodimer model, which is composed of 2-(9-anthracene)ureido-6-(1-undecyl)-4[1H]-pyrimidinone (UPAn) with quadruple intermolecular and single intramolecular hydrogen bonds (HBs), have been examined using ultrafast two-dimensional infrared (2D IR) and steady-state IR spectroscopies. A less structurally fluctuating intermolecular HB is found between the pyrimidinone C═O and ureido N-H groups. However, a larger structurally fluctuating intramolecular HB is suggested by the equilibrium and dynamical line-shape measurements of the ureido C═O stretch. Further, dynamical time-dependent 2D IR diagonal and off-diagonal signals show that intra- and intermolecular vibrational energy transfer processes occur on the picosecond timescale, where the latter is more efficient due to intermolecular hydrogen bonding interaction and through-space interaction.

Intermolecular vibrational energy transfers in nitro-energetic molecules: A first-principles molecular dynamics study

Energy transfer plays an important role in the preservation and application of energetic molecules. An atomic-level understanding is necessary to delineate the chemical reaction mechanism, aiming at the possible modulation of related processes. In this work, by exciting the C–H stretching motion of nitromethanes, we studied intermolecular vibrational energy transfer by first-principles molecular dynamics (MD). It was observed for the first time that intramolecular vibrational energy redistribution (IVR) can be slower than intermolecular energy transfer in this system. More importantly, the energy-transfer process could lead to conformational rearrange. These findings offer a guidance for modulating the energy-transfer process and provide a theoretical basis for better understanding intermolecular vibrational energy transfer in energetic systems.

Plasmonic Substrates Do Not Promote Vibrational Energy Transfer at Solid-Liquid Interfaces.

Intermolecular vibrational energy transfer in monolayers of isotopically mixed rhenium carbonyl complexes at solid-liquid interfaces is investigated with the help of ultrafast 2D Attenuated Total Reflectance Infrared (2D ATR IR) spectroscopy in dependence of plasmonic surface enhancement effects. Dielectric and plasmonic materials are used to demonstrate that plasmonic effects have no impact on the vibrational energy transfer rate in a regime of moderate IR surface enhancement (enhancement factors up to ca. 30). This result can be explained with the common image-dipole picture. The vibrational energy transfer rate thus can be used as a direct observable to determine intermolecular distances on surfaces, regardless of their plasmonic properties.

NOESY-Like 2D-IR Spectroscopy Reveals Non-Gaussian Dynamics.

We have identified an unexpected signature of non-Gaussian dynamics in a conventional 2D IR measurement on a system with rapid intermolecular vibrational energy transfer. In a ternary mixture of the CO2 reduction photocatalyst, ReCl(bpy)(CO)3, NaSCN, and THF solvent, preferential association between the metal carbonyl catalyst and the NaSCN ion pairs facilitates intermolecular energy transfer on a few picoseconds time scale. Monitoring the cross peak between the highest frequency metal carbonyl band and the CN bands of NaSCN contact ion pairs, we find a striking time evolution of the cross-peak position on the detection axis. This frequency shift, which is due to spectral diffusion following intermolecular energy transfer, occurs with a time scale that is distinct from either the donor or acceptor spectral diffusion measured simultaneously. We argue that the energy transfer, a second-order Förster process, effectively increases the dimensionality of the 2D-IR spectroscopy and thus enables sensitivity to non-Gaussian dynamics.

Effect of Hydrogen Bonds on the Vibrational Relaxation and Orientational Relaxation Dynamics of HN3 and N3(-) in Solutions.

Hydrogen bonds (H-bonds) play an important role in determining the structures and dynamics of molecular systems. In this work, we investigated the effect of H-bonds on the vibrational population relaxation and orientational relaxation dynamics of HN3 and N3(-) in methanol (CH3OH) and N,N-dimethyl sulfoxide (DMSO) using polarization-controlled infrared pump-probe spectroscopy and quantum chemical calculations. Our detailed analysis of experimental and computational results reveals that both vibrational population relaxation and orientational relaxation dynamics of HN3 and N3(-) in CH3OH and DMSO are substantially dependent on the strength of the H-bonds between the probing solute and its surrounding solvent. Especially in the case of N3(-) in CH3OH, the vibrational population relaxation of N3(-) is found to occur by a direct intermolecular vibrational energy transfer to CH3OH due to large vibrational coupling strength. The orientational relaxation dynamics of HN3 and N3(-), which are well fit by a biexponential function, are analyzed by the wobbling-in-a-cone model and extended Debye-Stokes-Einstein equation. Depending on the intermolecular interactions, the slow overall orientational relaxation occurs under slip, stick, and superstick boundary conditions. For HN3 and N3(-) in CH3OH and DMSO, the vibrational population relaxation becomes faster but the orientational relaxation becomes slower as the H-bond strength is increased. Our current results imply that H-bonds have significant effects on the vibrational population relaxation and orientational relaxation dynamics of a small solute whose size is comparable to the size of the solvent.

Intermolecular Vibrational Energy Transfers in Melts and Solutions

Resonant and nonresonant intermolecular vibrational energy transfers in Gdm-SCN/KSCN=1/1, GdmSCN/KS13CN=1/1 and GdmSCN/KS13C15N=1/1 mixed crystals in melts and in aqueous solutions are studied with the two dimensional infrared spectroscopy. The energy transfers in the samples are slower with a larger energy donor/acceptor gap, independent of the Raman spectra. The energy gap dependences of the nonresonant energy transfers cannot be described by the phonon compensation mechanism. Instead, the experimental energy gap dependences can be quantitatively described by the dephasing mechanism. Temperature dependences of resonant and nonresonant energy transfer rates in the melts are also consistent with the prediction of the dephasing mechanism. The series of results suggest that the dephasing mechanism can be dominant not only in solutions, but also in melts (pure liquids without solvents), only if the molecular motions (translations and rotations) are much faster than the nonresonant energy transfer processes.

Theoretical study of vibrational energy transfer of free OH groups at the water-air interface.

Recent experimental studies have shown that the vibrational dynamics of free OH groups at the water-air interface is significantly different from that in bulk water. In this work, by performing molecular dynamics simulations and mixed quantum/classical calculations, we investigate different vibrational energy transfer pathways of free OH groups at the water-air interface. The calculated intramolecular vibrational energy transfer rate constant and the free OH bond reorientation time scale agree well with the experiment. It is also found that, due to the small intermolecular vibrational couplings, the intermolecular vibrational energy transfer pathway that is very important in bulk water plays a much less significant role in the vibrational energy relaxation of the free OH groups at the water-air interface.

2D-IR spectroscopy of hydrogen-bond-mediated vibrational excitation transfer.

Vibrational excitation transfer along the hydrogen-bond-mediated pathways in the complex of methyl acetate (MA) and 4-cyanophenol (4CP) was studied by dual-frequency femtosecond two-dimensional infrared spectroscopy. We excited the energy-donating ester carbonyl stretching vibrational mode and followed the transfer to the energy-accepting benzene ring and cyano stretching vibrations. The complexes with no, one, and two hydrogen-bonded 4CP molecules were studied. Vibrational relaxation of the carbonyl mode is more efficient in both hydrogen-bonded complexes as compared with free MA molecules. The inter-molecular transport in a hydrogen-bonded complex involving a single 4CP molecule is slower than that in a complex with two 4CP molecules. In the former, vibrational relaxation leads to local heating, as shown by the spectroscopy of the carbonyl mode, whereas the local heating is suppressed in the latter because the excitation redistribution is more efficient. At early times, the transfer to the benzene ring is governed by its direct coupling with the energy-donating carbonyl mode, whereas at later times intermediate states are involved. The transfer to a more distant site of the cyano group in 4CP involves intermediate states at all times, since no direct coupling between the energy-donating and accepting modes was observed. We anticipate that our findings will be of importance for spectroscopic studies of bio-molecular structures and dynamics, and inter- and intra-molecular signaling pathways, and for developing molecular networking applications.