Vibronic Modes Research Articles

Theoretical Study on Vibrationally Resolved Electronic Spectra of Chiral Nanographenes.

Nanographenes are of increasing importance owing to their potential applications in the photoelectronic field. Meanwhile, recent studies have primarily focused on the pure electronic spectra of nanographenes, which have been found to be inadequate for describing the experimental spectra that contain vibronic progressions. In this study, we focused on the vibronic effect on the electronic transition of a range of chiral nanographenes, especially in the low-energy regions with distinct vibronic progressions, using theoretical calculations. All the calculations were performed at the PBE0-D3(BJ)/def2-TZVP level of theory, adopting both time-dependent and time-independent approaches with Franck-Condon approximation. The resulting calculated curves exhibited good alignment with the experimental data. Notably, for the nanographenes incorporating helicene units, owing to the increasing π-extension, the major vibronic modes in the vibrationally resolved spectra differed significantly from those of the primitive helicenes. This investigation suggests that calculations that account for the vibronic effect could have better reproducibility compared with calculations based solely on pure electronic transitions. We anticipate that this study could pave the way for further investigations into optical and chiroptical properties, with a deeper understanding of the vibronic effect, thereby providing theoretical explanations with higher precision on more sophisticated nanographenes.

Molecular jackhammers eradicate cancer cells by vibronic-driven action.

Through the actuation of vibronic modes in cell-membrane-associated aminocyanines, using near-infrared light, a distinct type of molecular mechanical action can be exploited to rapidly kill cells by necrosis. Vibronic-driven action (VDA) is distinct from both photodynamic therapy and photothermal therapy as its mechanical effect on the cell membrane is not abrogated by inhibitors of reactive oxygen species and it does not induce thermal killing. Subpicosecond concerted whole-molecule vibrations of VDA-induced mechanical disruption can be achieved using very low concentrations (500 nM) of aminocyanines or low doses of light (12 J cm-2, 80 mW cm-2 for 2.5 min), resulting in complete eradication of human melanoma cells in vitro. Also, 50% tumour-free efficacy in mouse models for melanoma was achieved. The molecules that destroy cell membranes through VDA have been termed molecular jackhammers because they undergo concerted whole-molecule vibrations. Given that a cell is unlikely to develop resistance to such molecular mechanical forces, molecular jackhammers present an alternative modality for inducing cancer cell death.

A Prototype Method for the Detection and Recognition of Pigments in the Environment Based on Optical Property Simulation.

The possibility of pigment detection and recognition in different environments such as solvents or proteins is a challenging, and at the same time demanding, task. It may be needed in very different situations: from the nondestructive in situ identification of pigments in paintings to the early detection of fungal infection in major agro-industrial crops and products. So, we propose a prototype method, the key feature of which is a procedure analyzing the lineshape of a spectrum. The shape of the absorption spectrum corresponding to this transition strongly depends on the immediate environment of a pigment and can serve as a marker to detect the presence of a particular pigment molecule in a sample. Considering carotenoids as an object of study, we demonstrate that the combined operation of the differential evolution algorithm and semiclassical quantum modeling of the optical response based on a generalized spectral density (the number of vibronic modes is arbitrary) allows us to distinguish quantum models of the pigment for different solvents. Moreover, it is determined that to predict the optical properties of monomeric pigments in protein, it is necessary to create a database containing, for each pigment, in addition to the absorption spectra measured in a predefined set of solvents, the parameters of the quantum model found using differential evolution.

Spectral fingerprints of individual Mn2+ impurities and Mn2+ pairs in magic-sized nanoclusters.

The chemical synthesis of (CdSe)13 magic-sized clusters (MSCs) allows the replacement of host atoms by individual transition metals such as Mn. By analyzing the spectral fingerprints of the Mn2+ photoluminescence (PL) in MSCs with different dopant concentrations, we are able to distinguish between single Mn2+ ions and coupled Mn2+ pairs. In case of Mn2+ pair emission, temperature-dependent studies show a pronounced red shift, followed by a distinct blue shift of the PL energy upon heating. This is related to a spin ladder formation of the ground and excited states due to Mn2+-Mn2+ exchange interaction at cryogenic temperatures, which is assumed to vanish at higher temperatures. In contrast, single Mn2+ ion PL exhibits a unique redshift with increasing temperature, which can be attributed to a particularly strong coupling to vibronic modes due to the ultimate small size of the MSCs.

Two-Dimensional Electronic Spectroscopy Reveals Vibrational Modes Coupled to Charge Transfer in a Julolidine-BODIPY Dyad.

Understanding charge transfer (CT) dynamics in molecular donor-acceptor (D-A) dyads can provide insight into developing efficient D-A molecules for capturing solar energy. Here, we characterize the excited-state evolution of a julolidine-BODIPY (Jul-BD) D-A system with an emissive CT state using time-resolved fluorescence, femtosecond transient absorption, and two-dimensional electronic spectroscopies. Comparison of these results with those from phenyl-BODIPY (Ph-BD) allows us to identify the dynamics at play during CT state formation and its subsequent conversion to either a fully charge-separated or triplet state. Photoexcitation of Jul-BD in tetrahydrofuran results in the formation of an initial emissive CT state that relaxes before fully charge-separating. In contrast, Jul-BD in toluene exhibits similar CT state dynamics, albeit at slower timescales, before decaying to a terminal triplet species. Quantum beat analysis at early times in both solvents shows several vibronic modes, which are corroborated using density functional theory (DFT) calculations. For Ph-BD, a single 220 cm-1 compression mode about the single bond linking the phenyl to BODIPY modulates their orbital overlap. Three active vibronic modes, 147, 174, and 214 cm-1, are found in Jul-BD, regardless of the dielectric constant of the medium. These motions correspond to compression and torsional motions along the single bond joining Jul to BD and are responsible for the evolution of the spontaneous and stimulated emission features in the time-resolved spectroscopic data, which is further supported by time-dependent DFT calculations of the steady-state absorption spectrum of the Jul-BD as a function of increasing D-A dihedral core angle. These findings show how torsional and compression motions can play a pivotal role in intramolecular CT between a D and an A linked by a single bond.

QuTiP-BoFiN: A bosonic and fermionic numerical hierarchical-equations-of-motion library with applications in light-harvesting, quantum control, and single-molecule electronics

The "hierarchical equations of motion" (HEOM) method is a powerful exact numerical approach to solve the dynamics and find the steady-state of a quantum system coupled to a non-Markovian and non-perturbative environment. Originally developed in the context of physical chemistry, it has also been extended and applied to problems in solid-state physics, optics, single-molecule electronics, and biological physics. Here we present a numerical library in Python, integrated with the powerful QuTiP platform, which implements the HEOM for both bosonic and fermionic environments. We demonstrate its utility with a series of examples. For the bosonic case, we include demonstrations of fitting arbitrary spectral densities, and an example of the dynamics of energy transfer in the Fenna-Matthews-Olson photosynthetic complex, showing how a suitable non-Markovian environment can protect against pure dephasing. We also demonstrate how the HEOM can be used to benchmark different strategies for dynamical decoupling of a spin from its environment, and show that the Uhrig pulse-spacing scheme is less optimal than equally spaced pulses when the environment's spectral density is very broad. For the fermionic case, we present an integrable single-impurity example, used as a benchmark of the code, and a more complex example of an impurity strongly coupled to a single vibronic mode, with applications to single-molecule electronics.

Topological Frenkel exciton polaritons in one-dimensional lattices of strongly coupled cavities

Frenkel polaritons, hybrid light-matter quasiparticles, offer promise for the designing of new optoelectronic devices. However, their technological implementations are hindered by sensitivity to imperfections. Topology has been raised as a way to circumvent defects and fabrication limitations. Here, we propose a lattice of cavities to realize the one-dimensional Su-Schrieffer-Heeger model (SSH) for topological Frenkel polaritons. By engineering the configuration of the cavities we demonstrate that the SSH topological and trivial phases can be accessed, which we unravel by employing a dual approach based on classical and quantum theories. We study the role of inherent vibron modes and fabrication defects in the robustness of the topological phases of polaritons. Our study demonstrates a simple experimentally realistic setup to realize topological polaritons at room temperature.

Differential evolution reveals the effect of polar and nonpolar solvents on carotenoids: A case study of astaxanthin optical response modeling

• Unique software that simulates optical response of biological pigments was developed • Differential evolution is used for finding the best model to fit experimental data • Multimode Brownian oscillator models were created to simulate carotenoid absorption • The optimal settings of Differential evolution allowing fast convergence were found • Differential evolution allowed distinguishing models for polar and nonpolar solvents The task to simulate realistic absorption spectra of electronic transitions in pigment molecules takes the form of the art of optimization, particularly if one must choose between the quality of the results obtained and the calculation time necessary to get such quality. The semiclassical theory of optical response provides us with a good opportunity to escape a so-called sum-over-state procedure of considering the innumerable number of vibronic states of a pigment by applying a correlation function approach. This approach, known as the multimode Brownian oscillator model (MBOM), involves replacing an infinite set of vibronic states, which interacts with an electronic transition, with a finite set of effective vibronic modes. Thus, the parameters of effective vibronic modes and an electronic transition can be found only by fitting experimental data. This situation gives rise to the following problem: as the number of free parameters increases, it becomes more difficult to find a single solution. To overcome this obstacle, differential evolution (DE), a method of global optimization, which is based on the idea of natural selection, seems to be the right choice. To test the efficiency of DE in solving quantum mechanical problems, we simulated absorption spectra of astaxanthin (AST) in 18 different organic solvents by using the MBOM. To do so, we developed software that implements both the DE algorithm and linear absorption modeling procedures. We have shown that simulating practically identical AST spectra, DE allows determining the effect of polar and nonpolar solvents on several parameters of MBOM of AST with high accuracy.

Quantum tunnelling in the context of SARS-CoV-2 infection

The SARS-CoV-2 pandemic has added new urgency to the study of viral mechanisms of infection. But while vaccines offer a measure of protection against this specific outbreak, a new era of pandemics has been predicted. In addition to this, COVID-19 has drawn attention to post-viral syndromes and the healthcare burden they entail. It seems integral that knowledge of viral mechanisms is increased through as wide a research field as possible. To this end we propose that quantum biology might offer essential new insights into the problem, especially with regards to the important first step of virus-host invasion. Research in quantum biology often centres around energy or charge transfer. While this is predominantly in the context of photosynthesis there has also been some suggestion that cellular receptors such as olfactory or neural receptors might employ vibration assisted electron tunnelling to augment the lock-and-key mechanism. Quantum tunnelling has also been observed in enzyme function. Enzymes are implicated in the invasion of host cells by the SARS-CoV-2 virus. Receptors such as olfactory receptors also appear to be disrupted by COVID-19. Building on these observations we investigate the evidence that quantum tunnelling might be important in the context of infection with SARS-CoV-2. We illustrate this with a simple model relating the vibronic mode of, for example, a viral spike protein to the likelihood of charge transfer in an idealised receptor. Our results show a distinct parameter regime in which the vibronic mode of the spike protein enhances electron transfer. With this in mind, novel therapeutics to prevent SARS-CoV-2 transmission could potentially be identified by their vibrational spectra.

Interplay of the Jahn-Teller effect and spin-orbit coupling: The case of trigonal vibrations

We study an interplay between the orbital degeneracy and spin-orbit coupling giving rise to spin-orbital entangled states. As a specific example, we analyze the interaction of electrons occupying triply degenerate single-ion $t_{2g}$ levels with trigonal vibronic modes (the $t\otimes T$ problem). A more general problem of the electron-lattice interaction involving both tetragonal and trigonal vibrations is also considered. It is shown that the result of such interaction crucially depends on the occupation of $t_{2g}$ levels leading to either the suppression or enhancement of the Jahn-Teller effect by the spin-orbit coupling.

All-experimental analysis of doubly resonant sum-frequency generation spectra for Franck–Condon and Herzberg–Teller vibronic modes

The transform technique applied to the analysis of doubly resonant sum-frequency generation (DR-SFG) spectra is extended to include Herzberg-Teller (HT) vibronic modes. The experimentally measured overlap spectral function generates all the energy resonant amplitudes of the DR-SFG excitation function for both Franck-Condon (FC) and HT modes. When FC modes dominate the DR-SFG spectra, a methodology is provided to perform efficient curve fitting and orientation analysis in order to extract FC activities of the various vibration modes from experimental spectra with the help of a molecular model. Determination of the FC or HT natures of the vibration modes from DR-SFG data is also shown to be possible through their visible line shapes with an appropriate choice of polarizations. As an example, experimental DR-SFG data suggest that a known HT-active mode in the vibronic structure of Rhodamine 6G monomers exhibits a FC behavior in molecular aggregates.

Vibrations Responsible for Luminescence from HJ-Aggregates of Conjugated Polymers Identified by Cryogenic Spectroscopy of Single Nanoparticles.

A single polymer chain can be thought of as a covalently bound J-aggregate, where the microscopic transition-dipole moments line up to emit in phase. Packing polymer chains into a bulk film can result in the opposite effect, inducing H-type coupling between chains. Cofacial transition-dipole moments oscillate out of phase, canceling each other out, so that the lowest-energy excited state turns dark. H-aggregates of conjugated polymers can, in principle, be coaxed into emitting light by mixing purely electronic and vibronic transitions. However, it is challenging to characterize this electron-phonon coupling experimentally. In a bulk film, many different conformations exist with varying degrees of intrachain J-type and interchain H-type coupling strengths, giving rise to broad and featureless aggregate absorption and emission spectra. Even if single nanoparticles consisting of only a few single chains are grown in a controlled fashion, the luminescence spectra remain broad, owing to the underlying molecular dynamics and structural heterogeneity at room temperature. At cryogenic temperatures, emission from H-type aggregates should be suppressed because, in the absence of thermal energy, internal conversion drives the aggregate to the lowest-energy dark state. At the same time, electronic and vibronic transitions narrow substantially, facilitating the attribution of spectral signatures to distinct vibrational modes. We demonstrate how to distinguish signatures of interchain H-type aggregate species from those of intramolecular J-type coupling. Whereas all dominant vibronic modes revealed in the photoluminescence (PL) and surface-enhanced resonance Raman scattering spectra of a single chromophore within a single polymer chain are identified in the J-type aggregate luminescence spectra, they are not all present at once in the H-type spectra. Universal spectral features are found for the luminescence from strongly HJ-coupled chains, clearly resolving the vibrations responsible for the nonadiabatic excited-state molecular dynamics that enable light emission. We discuss the possible combinations of vibrational modes responsible for H-type aggregate PL and demonstrate that only one, mainly the lowest energy one, of the three dominant vibrational modes contributes to the 0-1 transition, whereas combinations of all three are found in the 0-2 transition. From this analysis, we can distinguish between energy shifts due to either J-type intrachain coupling or H-type interchain interactions, offering a means to directly discriminate between structural and energetic disorder.

Evidence for a High-Pressure Isostructural Transition in Nitrogen

We observed an isostructural phase transition in the solid nitrogen λ-N2 at approximately 50 GPa accompanied by anomalies in lattice parameters, atomic volume and Raman vibron modes. The anomalies are ascribed to a slight reorientation of the nitrogen molecules, which does not seem to affect the monoclinic symmetry (space group P21/c). Our ab initio calculations further confirm the phenomena, and suggest an optimized structure for the λ-N2 phase. In addition, a new high-pressure amorphous phase of η′-N2 was also discovered by a detailed investigation of the pressure-temperature phase diagram of nitrogen with the aim of probing the phase stability of λ-N2. Our result may provide helpful information about the crystallographic nature of dissociation transitions in diatomic molecular crystals (H2, O2, N2, etc).

S1-State Decay Dynamics of Benzenediols (Catechol, Resorcinol, and Hydroquinone) and Their 1:1 Water Clusters.

The S1-state decaying rates of the three different benzenediols, catechol, resorcinol, and hydroquinone, and their 1:1 water clusters have been state-specifically measured using the picosecond time-resolved parent ion transients obtained by the pump (excitation) and probe (ionization) scheme. The S1 lifetime of catechol is found to be short, giving τ ∼ 5.9 ps at the zero-point level. This is ascribed to the H-atom detachment from the free OH moiety of the molecule. Consistent with a previous report (J. Phys. Chem. Lett. 2013, 4, 3819-3823), the S1 lifetime gets lengthened with low-frequency vibrational mode excitations, giving τ ∼ 9.0 ps for the 116 cm-1 band. The S1 lifetimes at the additional vibronic modes of catechol are newly measured, showing the nonnegligible mode-dependent fluctuations of the tunneling rate. When catechol is complexed with water, the S1 lifetime is enormously increased to τ ∼ 1.80 ns at the zero-point level while it shows an unusual dip at the intermolecular stretching mode excitation (τ ∼ 1.03 ns at 146 cm-1). Otherwise, it is shortened monotonically with increasing the internal energy, giving τ ∼ 0.67 ns for the 856 cm-1 band. Two different asymmetric or symmetric conformers of resorcinol give the respective S1 lifetimes of 4.5 or 6.3 ns at their zero-point levels according to the estimation from our transients taken within the temporal window of 0-2.7 ns. When resorcinol is 1:1 complexed with H2O, the S1 decaying rate is slightly accelerated for both conformers. The S1 lifetimes of trans and cis forms of hydroquinone are measured to be more or less same, giving τ ∼ 2.8 ns at the zero-point level. When H2O is complexed with hydroquinone, the S1 decaying process is facilitated for both conformers, slightly more efficiently for the cis conformer.

Crystal-field excitations and vibronic modes in the triangular-lattice spin-liquid candidate TbInO3

We study the ground-state properties, the electronic excitations, and lattice dynamics in spin-liquid candidate ${\mathrm{TbInO}}_{3}$. By employing polarization-resolved Raman spectroscopy we define the intermultiplet and intramultiplet excitations, and establish the low-energy crystal-field (CF) level scheme. In particular, we demonstrate that the ground state of the ${\mathrm{Tb}}^{3+}$ ions is a non-Kramers doublet, and relate the enhanced linewidth of the CF modes to the magnetic fluctuations near the spin-liquid ground state. We identify the 38 allowed Raman-active phonon modes at low temperature. Moreover, we observe hybrid vibronic excitations involving coupled CF and low-lying phonon modes, suggesting strong spin-lattice dynamics. We develop a model for vibronic states and obtain the parameters of the bare responses and coupling strength. We further demonstrate that the obtained CF level scheme is consistent with specific-heat data.

Efficient DNA-Driven Nanocavities for Approaching Quasi-Deterministic Strong Coupling to a Few Fluorophores.

Strong coupling between light and matter is the foundation of promising quantum photonic devices such as deterministic single photon sources, single atom lasers, and photonic quantum gates, which consist of an atom and a photonic cavity. Unlike atom-based systems, a strong coupling unit based on an emitter-plasmonic nanocavity system has the potential to bring these devices to the microchip scale at ambient conditions. However, efficiently and precisely positioning a single or a few emitters into a plasmonic nanocavity is challenging. In addition, placing a strong coupling unit on a designated substrate location is a demanding task. Here, fluorophore-modified DNA strands are utilized to drive the formation of particle-on-film plasmonic nanocavities and simultaneously integrate the fluorophores into the high field region of the nanocavities. High cavity yield and fluorophore coupling yield are demonstrated. This method is then combined with e-beam lithography to position the strong coupling units on designated locations of a substrate. Furthermore, polariton energy under the detuning of fluorophore embedded nanocavities can fit into a model consisting of three sets of two-level systems, implying vibronic modes may be involved in the strong coupling. Our system makes strong coupling units more practical on the microchip scale and at ambient conditions and provides a stable platform for investigating fluorophore-plasmonic nanocavity interaction.

All-experimental analysis of doubly resonant sum-frequency generation spectra: Application to aggregated rhodamine films.

A new method is proposed to analyze Doubly Resonant infrared-visible Sum-Frequency Generation (DR-SFG) spectra. Based on the transform technique, this approach is free from assumptions about vibronic modes, energies, or line widths and accurately captures through the overlap spectral function all required aspects of the vibronic structure from simple experimental linear absorption spectra. Details and implementation of the method are provided along with three examples treating rhodamine thin films about one monolayer thick. The technique leads to a perfect agreement between experiment and simulations of the visible DR-SFG line shapes, even in the case of complex intermolecular interactions resulting from J-aggregated chromophores in heterogeneous films. For films with mixed H- and J-aggregates, separation of their responses shows that the J-aggregate DR-SFG response is dominant. Our analysis also accounts for the unexplained results published in the early times of DR-SFG experiments.

Intrinsic Vibrational Angular Momentum from Nonadiabatic Effects in Noncollinear Magnetic Molecules.

We show that in noncollinear magnetic molecules, nonadiabatic (dynamical) effects due to the electron-vibron coupling are time-reversal symmetry breaking interactions for the vibrational field. Because the electronic wave function cannot be chosen as real in these molecules, a nonzero geometric vector potential (Berry connection) arises. As a result, an intrinsic nonzero vibrational angular momentum occurs even for nondegenerate modes and in the absence of external probes. The vibronic modes can then be seen as elementary quantum particles carrying a sizeable angular momentum. As a proof of concept, we demonstrate the magnitude of this topological effect by performing nonadiabatic first principles calculations on platinum clusters and by showing that these molecules host sizeable intrinsic phonon angular momenta comparable to the orbital electronic ones in itinerant ferromagnets.

Investigation of nonadiabatic coupling and diabatic electronic population dynamics on F2O+ cation within multi reference configuration interaction calculations

AbstractIn F2O+ cation the first (2B2) and second excited (2A1) electronic states can be coupled with each other by anti‐symmetric stretching mode and thus conical intersection and non‐adiabatic dynamics play an important role in characterizing molecular properties. In this work, we tried to find a suitable computational method for determining equilibrium structures and harmonic vibrational frequencies of the three lowest electronic states of F2O+. To understand non‐adiabatic dynamics at conical intersections, we calculated the probability of electronic population on 2B2 and 2A1 excited electronic states using linear vibronic coupling Hamiltonian mode including all three vibrational modes (bending (ω1), symmetric stretching (ω2) and anti‐symmetric stretching (ω3)).The amount of vibronic coupling constant between these states is obtained 0.08 eV at multi reference configuration interaction/Aug‐cc‐pVQZ level of theory.

Influence of Alkaline Earth Metal Ions on Structures and Luminescent Properties of NamMnUO2(CO3)3(4-m-2n)- (M = Mg, Ca; m, n = 0-2): Time-Resolved Fluorescence Spectroscopy and Ab Initio Studies.

The luminescence spectra of triscarbonatouranyl complexes were determined by experimental and theoretical methods. Time-resolved laser-induced fluorescence spectroscopy was used to monitor spectra of uranyl and bicarbonate solutions at 0.1 mol kgw-1 ionic strength and pH ca. 8. The concentrations of Mg2+ and Ca2+ in the samples were chosen in order to vary the proportions of the alkaline earth ternary uranyl complexes MgUO2(CO3)32-, CaUO2(CO3)32-, and Ca2UO2(CO3)3. The luminescence spectrum of each complex was determined by decomposition in order to compare it with the simulated spectra of model structures NamMnUO2(CO3)3(4-m-2n)- (M = Mg, Ca; m, n = 0-2) obtained by quantum chemical methods. The density functional theory (DFT) and time-dependent (TD)-DFT methods were used with the PBE0 functional to optimize the structures in the ground and excited states, respectively, including relativistic effects at the spin-free level, and water solvent effects using a continuum polarizable conductor model. The changes in the structural parameters were quantified with respect to the nature and the amount of alkaline earth counterions to explain the luminescence spectra behavior. The first low-lying excited state was successfully computed, together with the vibrational harmonic frequencies. The DFT calculations confirmed that uranyl luminescence originates from electronic transitions from one of the four nonbonding 5f orbitals of uranium to an orbital that has a uranyl-σ (5f, 6d) character mixed with the 2p atomic orbitals of the carbonate oxygens. Additional single-point calculations using the more accurate TD-DFT/CAM-B3LYP allow one to determine the position of the luminescence "hot band" for each structure in the range 467-476 nm and compared fairly well with experimental reports at around 465 nm. The complete luminescence spectra were built from theoretical results with the corresponding assignment of the electronic transitions and vibronic modes involved, mainly the U-Oax stretching mode. The resulting calculated spectra showed a very good agreement with experimental band positions and band spacing attributed to MgUO2(CO3)32-, CaUO2(CO3)32-, and Ca2UO2(CO3)3. The evolution of luminescence intensities with the number of alkaline earth metal ions in the structure was also correctly reproduced.