Assessing the Determinants of Cavity Polariton Relaxation Using Angle-Resolved Photoluminescence Excitation Spectroscopy.

The strong coupling of light and matter within electromagnetic resonators leads to the formation of cavity polaritons whose hybrid nature may help certain ground and excited state chemical processes. To help enable the development of polariton chemistry, we have developed and applied a spectroscopic technique to leverage the relatively larger spatial coherence of polaritons to assess the determinants of relaxation in hybrid light-matter states. By exciting the lower polariton (LP) state in cavity samples filled with different metalloporphyrin chromophores, we measured and modeled angle-resolved photoluminescence excitation spectra. Our results suggest that the shortest lived constituent of the LP state characterized by specific Hopfield coefficients limits the light absorption of the intracavity molecules, which we equate with the effective polariton lifetime. Our results suggest that researchers need to consider the lifetimes of both photons and excitons participating in strong light-matter coupling when designing polaritonic systems and the methods they can use to assess the relaxation of polaritonic states.

Decorrelated singlet and triplet exciton delocalization in acetylene-bridged Zn-porphyrin dimers.

The controlled delocalization of molecular excitons remains an important goal towards the application of organic chromophores in processes ranging from light-initiated chemical transformations to classical and quantum information processing. In this study, we present a methodology to couple optical and magnetic spectroscopic techniques and assess the delocalization of singlet and triplet excitons in model molecular chromophores. By comparing the steady-state and time-resolved optical spectra of Zn-porphyrin monomers and weakly coupled dimers, we show that we can use the identity of substituents bound at specific positions of the macromolecules' rings to control the inter-ring delocalization of singlet excitons stemming from their B states through acetylene bridges. While broadened steady-state absorption spectra suggest the presence of delocalized B state excitons in mesityl-substituted Zn-tetraphenyl porphyrin dimers (Zn2U-D), we confirm this conclusion by measuring an enhanced ultrafast non-radiative relaxation from these inter-ring excitonic states to lower lying electronic states relative to their monomer. In contrast to the delocalized nature of singlet excitons, we use time-resolved EPR and ENDOR spectroscopies to show that the triplet states of the Zn-porphyrin dimers remain localized on one of the two macrocyclic sub-units. We use the analysis of EPR and ENDOR measurements on unmetallated model porphyrin monomers and dimers to support this conclusion. The results of DFT calculations also support the interpretation of localized triplet states. These results demonstrate researchers cannot conclude triplet excitons delocalize in macromolecular based on the presence of spatially extended singlet excitons, which can help in the design of chromophores for application in spin conversion and information processing technologies.

Motional Narrowing through Photonic Exchange: Rational Suppression of Excitonic Disorder from Molecular Cavity Polariton Formation.

Maximizing the coherence between the constituents of molecular materials remains a crucial goal toward the implementation of these systems into everyday optoelectronic technologies. Here we experimentally assess the ability of strong light-matter coupling in the collective limit to reduce energetic disorder using porphyrin-based chromophores in Fabry-Pérot (FP) microresonator structures. Following characterization of cavity polaritons formed from chemically distinct porphyrin dimers, we find that the peaks corresponding to the lower polariton (LP) state in each sample do not possess widths consistent with conventional theories. We model the behavior of the polariton peak widths effectively using the results of spectroscopic theory. We correlate differences in the suppression of excitonic energetic disorder between our samples with microscopic light-matter interactions and propose that the suppression stems from photonic exchange. Our results demonstrate that cavity polariton formation can suppress disorder and show researchers how to design coherence into hybrid molecular material systems.

Evidence of defect-induced broadband light emission from 2D Ag-Bi double perovskites grown at liquid-liquid interfaces.

Controlling the light emission spectra of low-dimensional hybrid organic-inorganic materials remains an important goal toward the implementation of these materials into real-world optoelectronic devices. In this study, we present evidence that the self-assembly of two-dimensional (2D) silver bismuth iodide double perovskite derivatives at the interface of aqueous and organic solutions leads to the formation of defects capable of modulating the light emission spectra of these materials. Through an analysis of the structural parameters used to explain the photoluminescence (PL) spectra of 2D perovskites, we show the light spectra emitted by (4-ammonium methyl)piperidinium (4-AMP) and (3-ammonium methyl)pyridinium (3-AMPy)-spaced AgBiI8 double perovskites formed through interfacial solution-phase chemistry differ qualitatively and quantitatively from thin film samples. We use previous results to propose the differences observed in the PL spectra of different material morphologies stem from equatorial iodide vacancy formation driven by the kinetics of self-assembly at the liquid-liquid interface. These results show the generality of these chemical physics principles in the formation of defect sites in solution-processed semiconducting nanomaterials, which could help enable their broad use in optoelectronic technologies.

Light Emission from Vibronic Polaritons in Coupled Metalloporphyrin-Multimode Cavity Systems.

In this study, we explore how one can use cavity polariton formation and a non-Condon vibronic coupling mechanism to form a type of hybrid light-matter state we denote as Herzberg-Teller (HT) vibronic polaritons. We use simple models to define the basic characteristics of these hybrid light-matter excitations including their dispersive energies. Experimentally, we find evidence of HT polaritons in the light emission spectra from copper(II) tetraphenylporphyrin (CuTPP) molecules strongly coupled to both single and multimode Fabry-Perot resonator structures. For specific resonator designs, we find evidence of significant enhancement of light emission from a short-lived sing-doublet state of CuTPP, which couples to a higher energy singlet state via a non-Condon vibronic mechanism. The results of a two-state model support the conclusion that this enhancement and the temperature-dependent dispersion of the light emission peak energy stem from radiative relaxation into cavity photon states dressed by collective vibrations of the molecules participating in polariton formation. These results show how researchers can leverage the complex interplay of electronic and nuclear degrees of freedom in light absorbing molecules to form a vaster array of coherent light-matter states and potentially transform platforms in optoelectronic and photocatalytic technologies.

Local molecular probes of ultrafast relaxation channels in strongly coupled metalloporphyrin-cavity systems.

The quantum control of ultrafast excited state dynamics remains an unachieved goal within the chemical physics community. In this study, we assess how strongly coupling to cavity photons affects the excited state dynamics of strongly coupled zinc (II) tetraphenyl porphyrin (ZnTPP) and copper (II) tetraphenyl porphyrin (CuTPP) molecules. By varying the concentration of each chromophore within different Fabry-Pérot (FP) structures, we control the collective vacuum Rabi splitting between the energies of cavity polariton states formed through the strong coupling of molecular electrons and cavity photons. Using ultrafast transient reflectivity and transmission measurements probing optical transitions of individual ZnTPP and CuTPP molecules, we find that the polaritonic states localize into uncoupled excited states of these chromophores through different mechanisms. For ZnTPP, we build a simple kinetic model including a direct channel of relaxation between the polaritonic states. We find that our models necessitate a small contribution from this interpolaritonic relaxation channel to explain both our steady-state and transient optical spectroscopic measurements adequately. In contrast, we propose that strong cavity coupling slows the internal conversion between electronic states of CuTPP not directly interacting with the photons of FP structures. These results suggest that researchers must consider the vibrational structure and excited state properties of the strongly coupled chromophores when attempting to use polariton formation as a tool to control the dynamics of molecules central to photo-sensitizing and light harvesting applications.

Kinetic Molecular Cationic Control of Defect-Induced Broadband Light Emission in 2D Hybrid Lead Iodide Perovskites.

In this study, we examine the effects of changing organic cation concentrations on the efficiency and photophysical implications of exciton trapping in two-dimensional hybrid lead iodide self-assembled quantum wells (SAQWs). We show that increasing the concentration of alkyl and aryl ammonium cations causes the formation of SAQWs at a liquid-liquid interface to possess intense, broadband subgap photoluminescence (PL) spectra. Electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopic studies suggest that materials formed under these cation concentrations possess morphologies consistent with inhibited crystallization kinetics but exhibit qualitatively similar bulk chemical bonding to nonluminescent materials stabilized in the same structure from precursor solutions containing lower cation concentrations. Temperature- and power-dependent PL spectra suggest that the broadband subgap light emission stems from excitons self-trapped at defect sites, which we assign as edge-like, collective I vacancies using a simple model of the chemical equilibrium driving material self-assembly. These results suggest that changes to the availability of molecular cations can suitably control the light emission properties of self-assembled hybrid organic-inorganic materials in ways central to their applicability in lighting technologies.

Quantum Control of Ultrafast Internal Conversion Using Nanoconfined Virtual Photons.

The rational control of nonradiative relaxation remains an unfulfilled goal of synthetic chemistry. In this study, we show how strongly coupling an ensemble of molecules to the virtual photons of an electromagnetic cavity provides a rational handle over ultrafast, nonradiative dynamics. Specifically, we control the concentration of zinc tetraphenyl porphyrin molecules within nanoscale Fabry-Perot cavity structures to show a variable collective vacuum Rabi splitting between cavity polaritons coincides with systematic changes in internal conversion rates. We find these changes deviate from the predictions of so-called gap laws. We also show that simple theories of structural changes caused by polariton formation cannot explain discrepancies between our results and established theoretical predictions. In light of these deficiencies, we explore other ways to explain the dependence of the internal conversion rate on polariton parameters. Our results demonstrate cavity polariton formation controls the photophysics of light harvesting and photocatalytic molecular moieties and the gap remaining in our fundamental understanding of mechanisms enabling this control.

Room-Temperature Broadband Light Emission from Hybrid Lead Iodide Perovskite-Like Quantum Wells: Terahertz Spectroscopic Investigation of Metastable Defects.

The properties of mid-band-gap electronic states are central to the potential application of self-assembled, hybrid organic-inorganic perovskite-like quantum wells in optoelectronic technologies. We investigate broadband light emission from mid-band-gap states in fast-forming hybrid organic lead iodide quantum wells at room temperature. By comparing temperature- and intensity-dependent photoluminescence (PL) spectra emitted from butyl ammonium spaced inorganic layers, we propose that structural defects in a metastable material phase trap excitons and cause broadband light emission spanning wavelengths between 600 and 1000 nm. We use temperature-dependent terahertz time-domain spectroscopy to correlate changes in the subgap PL emission with changes in the chemical bonding of the inorganic octahedral layer. Our results provide new fundamental physical insights into the array of mechanisms capable of inducing broadband light emission from low-dimensional perovskite-like materials central to their application in future optoelectronic technologies and novel spectroscopic tools to characterize these states.

Defects Cause Subgap Luminescence from a Crystalline Tetracene Derivative.

We use steady-state and ultrafast nonlinear spectroscopies in combination with density functional theory calculations to explain light emission below the optical gap energy (Eo) of crystalline samples of 5,12-diphenyl tetracene (DPT). In particular, the properties of vibrational coherences imprinted on a probe pulse transmitted through a DPT single crystal indicate discrete electronic transitions below Eo of this organic semiconductor. Analysis of coherence spectra leads us to propose structural defect states give rise to these discrete transitions and subgap light emission. We use the polarization dependence of vibrational coherence spectra to tentatively assign these defects in our DPT samples. Our results provide fundamental insights into the properties of midgap states in organic materials important for their application in next-generation photonics and optoelectronics technologies.

Evidence of Ultrafast Charge Transfer Driven by Coherent Lattice Vibrations.

We report evidence that intermolecular vibrations coherently drive charge transfer between the sites of a material on ultrafast time scales. Following a nonresonant stimulated Raman pump pulse that excites the organic material quinhydrone, we observe the initial appearance of oscillations due to intermolecular lattice vibrations and then the delayed appearance of a higher-frequency oscillation that we assign to a totally symmetric intramolecular vibration. We use the coherent dynamics of the transient reflectivity signal to propose that coherence transfer drives excitation of this intramolecular vibration. Furthermore, we conclude that the dynamical frequency shift of the intramolecular vibration reports the formation of a quasi-stable charge-separated state on ultrafast time scales. We calculate model dynamics using the extended Hubbard Hamiltonian to explain coherence transfer due to vibrationally driven charge transfer. These results demonstrate that the coherent excitation of low-frequency vibrations can drive charge transfer in the solid state and control material properties.

Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid.

Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm(-1) oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

Energy cascades, excited state dynamics, and photochemistry in cob(III)alamins and ferric porphyrins.

Porphyrins and the related chlorins and corrins contain a cyclic tetrapyrrole with the ability to coordinate an active metal center and to perform a variety of functions exploiting the oxidation state, reactivity, and axial ligation of the metal center. These compounds are used in optically activated applications ranging from light harvesting and energy conversion to medical therapeutics and photodynamic therapy to molecular electronics, spintronics, optoelectronic thin films, and optomagnetics. Cobalt containing corrin rings extend the range of applications through photolytic cleavage of a unique axial carbon-cobalt bond, permitting spatiotemporal control of drug delivery. The photochemistry and photophysics of cyclic tetrapyrroles are controlled by electronic relaxation dynamics including internal conversion and intersystem crossing. Typically the electronic excitation cascades through ring centered ππ* states, ligand to metal charge transfer (LMCT) states, metal to ligand charge transfer (MLCT) states, and metal centered states. Ultrafast transient absorption spectroscopy provides a powerful tool for the investigation of the electronic state dynamics in metal containing tetrapyrroles. The UV-visible spectrum is sensitive to the oxidation state, electronic configuration, spin state, and axial ligation of the central metal atom. Ultrashort broadband white light probes spanning the range from 270 to 800 nm, combined with tunable excitation pulses, permit the detailed unravelling of the time scales involved in the electronic energy cascade. State-of-the-art theoretical calculations provide additional insight required for precise assignment of the states. In this Account, we focus on recent ultrafast transient absorption studies of ferric porphyrins and corrin containing cob(III)alamins elucidating the electronic states responsible for ultrafast energy cascades, excited state dynamics, and the resulting photoreactivity or photostability of these compounds. Iron tetraphenyl porphyrin chloride (Fe((III))TPPCl) exhibits picosecond decay to a metal centered d → d* (4)T state. This state decays on a ca. 16 ps time scale in room temperature solution but persists for much longer in a cryogenic glass. The photoreactivity of the (4)T state may lead to novel future applications for these compounds. In contrast, the nonplanar cob(III)alamins contain two axial ligands to the central cobalt atom. The upper axial ligand can be an alkyl group as in the two biologically active coenzymes or a nonalkyl ligand such as -CN in cyanocobalamin (vitamin B12) or -OH in hydroxocobalamin. The electronic structure, energy cascade, and bond cleavage of these compounds is sensitive to the details of the axial ligand. Nonalkylcobalamins exhibit ultrafast internal conversion to a low-lying state of metal to ligand or ligand to metal charge transfer character. The compounds are generally photostable with ground state recovery complete on a time scale of 2-7 ps in room temperature aqueous solution. Alkylcobalamins exhibit ultrafast internal conversion to an S1 state of d/π → π* character. Most compounds undergo bond cleavage from this state with near unit quantum yield within ∼100 ps. Recent theoretical calculations provide a potential energy surface accounting for these observations. Conformation dependent mixing of the corrin π and cobalt d orbitals plays a significant role in the observed photochemistry and photophysics.

Electronic State-Resolved Electron-Phonon Coupling in an Organic Charge Transfer Material from Broadband Quantum Beat Spectroscopy.

The coupling of electron and lattice phonon motion plays a fundamental role in the properties of functional organic charge-transfer materials. In this Letter we extend the use of ultrafast vibrational quantum beat spectroscopy to directly elucidate electron-phonon coupling in an organic charge-transfer material. As a case study, we compare the oscillatory components of the transient reflection (TR) of a broadband probe pulse from single crystals of quinhydrone, a 1:1 cocrystal of hydroquinone and p-benzoquinone, after exciting nonresonant impulsive stimulated Raman scattering and resonant electronic transitions using ultrafast pulses. Spontaneous resonance Raman spectra confirm the assignment of these oscillations as coherent lattice phonon excitations. Fourier transforms of the vibrational quantum beats in our broadband TR measurements allow construction of spectra that we show report the ability of these phonons to directly modulate the electronic structure of quinhydrone. These results demonstrate how coherent ultrafast processes can characterize the complex interplay of charge transfer and lattice motion in materials of fundamental relevance to chemistry, materials sciences, and condensed matter physics.

Ligand recruitment and spin transitions in the solid-state photochemistry of Fe(III)TPPCl.

We report evidence for the formation of long-lived photoproducts following excitation of iron(III) tetraphenylporphyrin chloride (Fe(III)TPPCl) in a 1:1 glass of toluene and CH(2)Cl(2) at 77 K. The formation of these photoproducts is dependent on solvent environment and temperature, appearing only in the presence of toluene. No long-lived product is observed in neat CH(2)Cl(2) solvent. A 2-photon absorption model is proposed to account for the power-dependent photoproduct populations. The products are formed in a mixture of spin states of the central iron(III) metal atom. Metastable six-coordinate high-spin and low-spin complexes and a five-coordinate high-spin complex of iron(III) tetraphenylporphyrin are assigned using structure-sensitive vibrations in the resonance Raman spectrum. These species appear in conjunction with resonantly enhanced toluene solvent vibrations, indicating that the Fe(III) compound formed following photoexcitation recruits a toluene ligand from the surrounding environment. Low-temperature transient absorption (TA) measurements are used to explain the dependence of product formation on excitation frequency in this photochemical model. The six-coordinate photoproduct is initially formed in the high-spin Fe(III) state, but population relaxes into both high-spin and low-spin state at 77 K. This is the first demonstration of coupling between the optical and magnetic properties of an iron-centered porphyrin molecule.