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Abstract: The real boundary integral equation method is used to solve a specific type of mixed boundary value problem in an enhanced theory of bending of elastic plates with transverse [...]

The electronic structure and excited states of the Na3F cluster are investigated using different approximate, but numerically efficient, computational schemes, such as a 2e hybrid quantum/classical pseudopotential model with full-configuration interaction or time-dependent density-functional theory. Various quantities such as geometries and transition energies are compared with results previously obtained by multireference configuration interaction calculations, taken as reference data. The potential energy surfaces of the lowest excited states are investigated and the finite-temperature absorption spectra are calculated. The good agreement with recent beam experiments [J.-M. L’Hermite, V. Blanchet, A. Le Padellec, B. Lamory, and P. Labastie, Eur. Phys. J. D 28, 361 (2004)] leads to the conclusion that the absorption spectrum observed experimentally corresponds to the lowest energy isomer which has a C2v planar rhombic geometry. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Short-time, excited-state dynamics of the lowest isomer of the Na3F cluster is studied theoretically in order to interpret the features of recent time-resolved pump-probe ionization experiments [J. M. L’Hermite, V. Blanchet, A. Le Padellec, B. Lamory, and P. Labastie, Eur. Phys. J. D 28, 361 (2004)]. In the present paper, we propose an identification of the vibrational motion responsible for the oscillations in the ion signal, on the basis of quantum mechanical wave packet propagations and classical trajectory calculations. The good agreement between experiment and theory allows for a clear interpretation of the detected dynamics. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

We report a good agreement between the shapes of tailored pulses obtained theoretically and experimentally by using the optimal-control theory and the closed-loop learning technique to maximize the ionization yield in NaK. The theoretical pulse shapes are found to be robust regarding the choice of the initial guess. We assign the leading features of the pulse shapes to processes underlying the optimal control and reveal the mechanism which involves an electronic transition followed by a direct two-photon process and sequential one-photon processes at later times. We show that the optimal control not only serves for maximizing the desired yield but also as a tool for the analysis and the identification of the responsible processes. [ABSTRACT FROM AUTHOR]

The 2p core-level electron binding energies of size-selected silicon cluster ions have been determined from soft x-ray photoionization efficiency curves. Local chemical shifts and global charging energy contributions to the 2p binding energy can be separated, because core-level and valence-band electron binding energies exhibit the same inverse radius dependence. The experimental 2p binding energy distributions show characteristic size-specific patterns that are well reproduced by the corresponding electronic density of states obtained from density functional theory modeling. These results demonstrate that 2p binding energies in silicon clusters are dominated by initial state effects, i.e., by the interaction with the local valence electron density, and can thus be used to corroborate structural assignments. [ABSTRACT FROM AUTHOR]

Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes 2 )- p -carborane ( B 2 p Cab ) with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the p -carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes 2 LUMO. Unlike dianions of other C 2 B 10 H 12 carboranes, which rearrange to a nido -form, two-electron reduction of B 2 p Cab leads to a rearrangement into a basket-shaped intermediate.

Nanoscale semiconductors with isolated spin impurities have been touted as promising materials for their potential use at the intersection of quantum, spin, and information technologies. Electron paramagnetic resonance (EPR) studies of spins in semiconducting carbon nanotubes have overwhelmingly focused on spins more strongly localized by sp3-type lattice defects. However, the creation of such impurities is irreversible and requires specific reactions to generate them. Shallow charge impurities, on the other hand, are more readily and widely produced by simple redox chemistry, but have not yet been investigated for their spin properties. Here, we use EPR to study p-doped (6,5) semiconducting single-wall carbon nanotubes (s-SWNTs) and elucidate the role of impurity-impurity interactions in conjunction with exchange and correlation effects for the spin behavior of this material. A quantitative comparison of the EPR signals with phenomenological modeling combined with configuration interaction electronic structure calculations of impurity pairs shows that orbital overlap, combined with exchange and correlation effects, causes the EPR signal to disappear due to spin entanglement for doping levels corresponding to impurity spacings of 14 nm (at 30 K). This transition is predicted to shift to higher doping levels with increasing temperature and to lower levels with increasing screening, providing an opportunity for improved spin control in doped s-SWNTs., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Spontaneous emission and internal conversion rates are calculated within harmonic approximations and compared to the results obtained within the semi-classical extended thawed Gaussian approximation (ETGA). This is the first application of the ETGA in the calculation of internal conversion and emission rates for real molecular systems, namely, formaldehyde, fluorobenzene, azulene, and a dicyano-squaraine dye. The viability of the models as black-box tools for prediction of spontaneous emission and internal conversion rates is assessed. All calculations were done using a consistent protocol in order to investigate how different methods perform without previous experimental knowledge using density functional theory (DFT) and time-dependent DFT (TD-DFT) with B3LYP, PBE0, ωB97XD, and CAM-B3LYP functionals. Contrasting the results with experimental data shows that there are further improvements required before theoretical predictions of emission and internal conversion rates can be used as reliable indicators for the photo-luminescence properties of molecules. We find that the ETGA performs rather similar to the vertical harmonical model. Including anharmonicities in the calculation of internal conversion rates has a moderate effect on the quantitative results in the studied systems. The emission rates are fairly stable with respect to computational parameters, but the internal conversion rate reveals itself to be highly dependent on the choice of the spectral line shape function, particularly the width of the Lorentzian function, associated with homogeneous broadening., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

Five chiral squaraine dimers were synthesized by fusing chiral indolenine semisquaraines with three different benzobisthiazole bridges. The thereby created squaraine dimers show a strong splitting of the lowest energy absorption bands caused by exciton coupling. The intensities of the two exciton transitions and the energetic splitting depend on the angle of the two squaraine moieties within the chromophore dimer. The electric circular dichroism spectra of the dimers show intense Cotton effects whose sign depends on the used squaraine chromophores. Sizable anisotropies g abs of up to 2.6 × 10 -3 could be obtained. TD-DFT calculations were used to partition the rotational strength into the three Rosenfeld terms where the electric-magnetic coupling turned out to be the dominant contribution while the exciton chirality term is much smaller. This is because the chromophore dimers are essentially planar but the angle between the electric transition dipole moment of one squaraine and the magnetic transition dipole moment of the other squaraine strongly deviates from 90°, which makes the dot product between the two moment vectors and, thus, the rotational strength substantial.

cis -Stilbene ( cis -St) is a well-known benchmark system for cis - trans photoisomerization. cis -St also produces 4a,4b-dihydrophenanthrene (DHP) in solution with a quantum yield of less than 0.19. The ring closure reaction, however, has never been identified for gaseous cis -St, and a recent computational simulation predicted the quantum yield of DHP to be only 0.04. In the present study, we identified an ultrafast ring closure reaction of gaseous cis -St for the first time using extreme ultraviolet time-resolved photoelectron spectroscopy. Surface hopping trajectory calculations at the SA3-XMS-CASPT2(2,2) level of theory reproduce the features of the observed time-resolved photoelectron spectra and predict the cis -St:DHP: trans -St branching ratio to be 0.55:0.41:0.04, in contrast with previous estimates. The results indicate that photoexcited cis -St favors ring closure over cis - trans isomerization under the isolated condition.

The theoretical prediction of the rates of nonradiative processes in molecules is fundamental in assessing their emissive properties. In this context, global harmonic models have been widely used to simulate vibronic spectra as well as internal conversion rates and to predict photoluminescence quantum yields. However, these simplified models suffer from the limitations that are inherent to the harmonic approximation and can have a severe effect on the calculated internal conversion rates. Therefore, the development of more accurate semiclassical methods is highly desirable. Here, we introduce a procedure for the calculation of nonradiative rates in the framework of the time-dependent semi-classical Extended Thawed Gaussian Approximation (ETGA). We systematically investigate the performance of the ETGA method by comparing it to the adiabatic and vertical harmonic methods, which belong to the class of widely used global harmonic models. Its performance is tested in potentials that cannot be treated adequately by global harmonic models, beginning with Morse potentials of varying anharmonicity followed by a double well potential. The calculated radiative and nonradiative internal conversion rates are compared to reference values based on exact quantum dynamics. We find that the ETGA has the capability to predict internal conversion rates in anharmonic systems with an appreciable energy gap, whereas the global harmonic models prove to be insufficient.

N-Doped polycyclic aromatic hydrocarbons have recently emerged as potential organic electronic materials. The function of such materials is determined not only by the intrinsic electronic properties of individual molecules but also by their supramolecular interactions in the solid state. Therefore, a proper characterization of the interactions between the individual units is of interest to materials science since they ultimately govern properties such as excitons and charge transfer. Here, we report a joint experimental and computational study of two azaphenanthrene dimers to determine the structure and the nature of supramolecular interactions in the aggregates. IR/UV double-resonance experiments were carried out using far- and mid-infrared free-electron laser radiation. The experimental spectra are compared with quantum chemical calculations for the lowest-energy π-stacked and hydrogen-bonded structures. The data reveal a preference of the π-stacked structure for the benzo[f]quinoline and the phenanthridine dimer.

Herein we present a systematic study demonstrating to which extent exciton formation can amplify fluorescence based on a series of ethylene-bridged oligo-BODIPYs. A set of non- and weakly fluorescent BODIPY motifs was selected and transformed into discrete, chain-like oligomers by linkage via a flexible ethylene tether. The prepared superstructures constitute excitonically active entities with non-conjugated, Coulomb-coupled oscillators. The non-radiative deactivation channels of Internal Conversion (IC), also combined with an upstream reductive Photoelectron Transfer (rPET) and Intersystem Crossing (ISC) were addressed at the monomeric state and the evolution of fluorescence and (non-)radiative decay rates studied along the oligomeric series. We demonstrate that a "masked" fluorescence can be fully reactivated irrespective of the imposed conformational rigidity. This work challenges the paradigm that a collective fluorescence enhancement is limited to sterically induced motional restrictions., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The understanding of excimer formation and its interplay with the singlet-correlated triplet pair state 1 (TT) is of high significance for the development of efficient organic electronics. Here, we study the photoinduced dynamics of the tetracene dimer in the gas phase by time-resolved photoionisation and photoion imaging experiments as well as nonadiabatic dynamics simulations in order to obtain mechanistic insight into the excimer formation dynamics. The experiments are performed using a picosecond laser system for excitation into the S 2 state and reveal a biexponential time dependence. The time constants, obtained as a function of excess energy, lie in the range between ≈10 ps and 100 ps and are assigned to the relaxation of the excimer on the S 1 surface and to its deactivation to the ground state. Simulations of the quantum-classical photodynamics are carried out in the frame of the semi-empirical CISD and TD-lc-DFTB methods. Both theoretical approaches reveal a dominating relaxation pathway that is characterised by the formation of a perfectly stacked excimer. TD-lc-DFTB simulations have also uncovered a second relaxation channel into a less stable dimer conformation in the S 1 state. Both methods have consistently shown that the electronic and geometric relaxation to the excimer state is completed in less than 10 ps. The inclusion of doubly excited states in the CISD dynamics and their diabatisation further allowed to observe a transient population of the 1 (TT) state, which, however, gets depopulated on a timescale of 8 ps, leading finally to the trapping in the excimer minimum., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

A protecting group strategy was employed to synthesise a series of indolenine squaraine dye oligomers up to the nonamer. The longer oligomers show a distinct solvent dependence of the absorption spectra, that is, either a strong blue shift or a strong red shift of the lowest energy bands in the near infrared spectral region. This behaviour is explained by exciton coupling theory as being due to H- or J-type coupling of transition moments. The H-type coupling is a consequence of a helix folding in solvents with a small Hansen dispersity index. DOSY NMR, small angle neutron scattering (SANS), quantum chemical and force field calculations agree upon a helix structure with an unusually large pitch and open voids that are filled with solvent molecules, thereby forming a kind of clathrate. The thermodynamic parameters of the folding process were determined by temperature dependent optical absorption spectra., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A series of distinct BODIPY heterooligomers (dyads, triads, and tetrads) comprising a variable number of typical green BODIPY monomers and a terminal red-emitting styryl-equipped species acting as an energy sink was prepared and subjected to computational and photophysical investigations in solvent media. An ethylene tether between the single monomeric units provides a unique foldameric system, setting the stage for a systematic study of excitation energy transfer processes (EET) on the basis of nonconjugated oscillators. The influence of stabilizing β-ethyl substituents on conformational space and the disorder of site energies and electronic couplings was addressed. In this way both the strong (Frenkel) and the weak (Förster) coupling limit could be accessed within a single system: the Frenkel limit within the strongly coupled homooligomeric green donor subunit and the Förster limit at the terminal heterosubstituted ethylene bridge. Femtosecond transient-absorption spectroscopy combined with mixed quantum-classical dynamic simulations demonstrate the limitations of the Förster resonance energy transfer (FRET) theory and provide a consistent framework to elucidate the trend of increasing relaxation lifetimes at higher homologues, revealing one of the fastest excitation energy transfer processes detected to date with a corresponding lifetime of 39 fs.

A squaraine heterotriad consisting of three different covalently linked squaraine chromophores was synthesized, and its absorption spectra were interpreted in terms of Kasha's exciton coupling theory. Using the exciton couplings derived from model dyads (ca. 700 cm -1 ) as the input, we were able to predict the exciton state energies of the heterotriad. Transient absorption spectroscopy with femtosecond time resolution showed that excitation of the highest exciton state populates a state mainly localized at one terminal squaraine chromophore, and energy transfer to the lowest exciton state localized at the other terminal squaraine occurs within 30 fs. Field-induced surface hopping dynamics simulations support the assumption of ultrafast energy transfer. Moreover, they show the close relationship between internal conversion and energy transfer in the intermediate to weak coupling regime. The latter is a consequence of excitation localization caused by molecular vibrations.

The electronic structure of the Au 2 + cation is essential for understanding its catalytic activity. We present the optical spectrum of mass-selected Au 2 + measured via photodissociation spectroscopy. Two vibrationally resolved band systems are observed in the 290-450 nm range (at ca. 440 and ca. 325 nm), which both exhibit rather irregular structure indicative of strong vibronic and spin-orbit coupling. The experimental spectra are compared to high-level quantum-chemical calculations at the CASSCF-MRCI level including spin-orbit coupling. The results demonstrate that the understanding of the electronic structure of this simple, seemingly H 2 + -like diatomic molecular ion strictly requires multireference and relativistic treatment including spin-orbit effects. The calculations reveal that multiple electronic states contribute to each respective band system. It is shown that popular DFT methods completely fail to describe the complex vibronic pattern of this fundamental diatomic cation., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Many nanotechnology materials rely on a hierarchical structure ranging from the nanometer scale to the micrometer scale. Their interplay determines the nanoscale optical coherence length, which plays a key role in energy transport and radiative decay and, thus, the optoelectronic applications. However, it is challenging to detect optical coherence length in multiscale structures with existing methods. Techniques such as atomic force microscopy and transmission electron microscopy are not sensitive to optical coherence length. Linear absorption and fluorescence spectroscopy methods, on the other hand, were generally limited by inhomogeneous broadening, which often obstructs the determination of nanoscale coherence length. Here, we carry out coherent two-dimensional microspectroscopy to obtain a map of the local optical coherence length within a hierarchically structured molecular film. Interestingly, the nanoscale coherence length is found to correlate with microscale topography, suggesting a perspective for controlling structural coherence on molecular length scales by appropriate microscopic growth conditions.

We report infrared spectra of xylylene isomers in the gas phase, using free electron laser (FEL) radiation. All xylylenes were generated by flash pyrolysis. The IR spectra were obtained by monitoring the ion dip signal, using a IR/UV double resonance scheme. A gas phase IR spectrum of para-xylylene  was recorded, whereas ortho- and meta-xylylene were found to partially rearrange to benzocyclobutene and styrene. Computations of the UV oscillator strength  for all molecules were carried out and provde an explanation for the observation of the isomerization products., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Fluorophores with high quantum yields are desired for a variety of applications. Optimization of promising chromophores requires an understanding of the non-radiative decay channels that compete with the emission of photons. We synthesized a new derivative of the famous laser dye 4-dicyanomethylen-2-methyl-6- p -dimethylaminostyryl-4 H -pyran ( DCM ), i.e. , merocyanine 4-(dicyanomethylene)-2- tert -butyl-6-[3-(3-butyl-benzothiazol-2-ylidene)1-propenyl]-4 H -pyran ( DCBT ). We measured fluorescence lifetimes and quantum yields in a variety of solvents and found a trend opposite to the energy gap law. This motivated a theoretical investigation into the possible non-radiative decay channels. We propose that a barrier to a conical intersection exists that is very sensitive to the solvent polarity. The conical intersection is characterized by a twisted geometry which allows a subsequent photoisomerization. Transient absorption measurements confirmed the formation of a photoisomer in unpolar solvents, while the measurements of fluorescence quantum yields at low temperature demonstrated the existence of an activation energy barrier., (This journal is © The Royal Society of Chemistry 2019.)

The photophysics of a molecular triad consisting of a BODIPY dye and two pyrene chromophores attached in 2-position are investigated by steady state and fs-time resolved transient absorption spectroscopy as well as by field induced surface hopping (FISH) simulations. While the steady state measurements indicate moderate chromophore interactions within the triad, the time resolved measurements show upon pyrene excitation a delocalised excited state which localises onto the BODIPY chromophore with a time constant of 0.12 ps. This could either be interpreted as an internal conversion process within the excitonically coupled chromophores or as an energy transfer from the pyrenes to the BODIPY dye. The analysis of FISH-trajectories reveals an oscillatory behaviour where the excitation hops between the pyrene units and the BODIPY dye several times until finally they become localised on the BODIPY chromophore within 100 fs. This is accompanied by an ultrafast nonradiative relaxation within the excitonic manifold mediated by the nonadiabatic coupling. Averaging over an ensemble of trajectories allowed us to simulate the electronic state population dynamics and determine the time constants for the nonradiative transitions that mediate the ultrafast energy transfer and exciton localisation on BODIPY.

Diborenes, R-BB-R', are of current interest in inorganic chemistry because they offer the opportunity to tune the properties of a biradical by modifying the substituents of the diborene parent, HBBH. Here we synthesize the elusive diborene by H atom abstraction from diborane, B 2 H 6 , using fluorine atoms and report a vibrationally resolved photoelectron spectrum of the HBBH biradical. The spectrum is interpreted by comparison with high-level ab initio computations, taking into account the Renner-Teller splitting in the X + 2 Π ionic ground state, which show an excellent agreement with the experimental spectrum. An adiabatic ionization energy of 9.080 ± 0.015 eV was determined, and a vibrational progression in the boron-boron stretching vibration of 0.14 eV is visible. This is due to the reduction of bond order upon ionization, accompanied by an increase of the computed boron-boron bond length, R BB , from 1.514 to 1.606 Å.