Nonadiabatic Exciton Dynamics and Energy Gradients in the Framework of FMO-LC-TDDFTB.

We introduce a novel methodology for simulating the excited-state dynamics of extensive molecular aggregates in the framework of the long-range corrected time-dependent density-functional tight-binding fragment molecular orbital method (FMO-LC-TDDFTB) combined with the mean-field Ehrenfest method. The electronic structure of the system is described in a quasi-diabatic basis composed of locally excited and charge-transfer states of all fragments. In order to carry out nonadiabatic molecular dynamics simulations, we derive and implement the excited-state gradients of the locally excited and charge-transfer states.

Onset of spin entanglement in doped carbon nanotubes studied by EPR.

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.

Full Electron Delocalization across the Cluster in 1,12-bisBMes--carborane Radical Anion.

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)--carborane () 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 -carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes LUMO.

A CASSCF/MRCI trajectory surface hopping simulation of the photochemical dynamics and the gas phase ultrafast electron diffraction patterns of cyclobutanone.

We present the simulation of the photochemical dynamics of cyclobutanone induced by the excitation of the 3 s Rydberg state. For this purpose, we apply the complete active space self-consistent field method together with the spin-orbit multireference configuration interaction singles treatment, combined with the trajectory surface hopping for the inclusion of nonadiabatic effects. The simulations were performed in the spin-adiabatic representation, including nine electronic states derived from three singlet and two triplet spin-diabatic states.

The Electronic Structures of Azaphenanthrenes and Their Dimers.

Insertion of a nitrogen atom modifies the electronic structures and photochemistry of polycyclic aromatic hydrocarbons by introducing nπ* states into the molecules. To better understand the electronic structures of isolated polycyclic aromatic nitrogen-containing hydrocarbons (PANHs) and their dimers as well as the influence of the position of the nitrogen atom in the molecule, we investigate three different azaphenanthrenes, benzo[]quinoline, benzo[]quinoline, and phenanthridine, in a joint experimental and computational study. Experimentally, resonance-enhanced multiphoton ionization (REMPI) spectroscopy is applied to characterize the excited electronic states.

Prediction of fluorescence quantum yields using the extended thawed Gaussian approximation.

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.

Simulation of exciton spectra in disordered supramolecular polymers: exciton localization in indolenine squaraine hexamers.

In order to understand the effects of disorder and defects in oligomers and polymers on the localization of excitons, we investigated the spectral properties of the squaraine B hexamer using long range corrected tight-binding TDDFT (lc-TDDFTB) and Frenkel-exciton model based calculations. Employing classical molecular dynamics, the indolenine squaraine hexamers helix was propagated in DCM and acetone to obtain ensembles of realistic structures, which naturally exhibit considerable disorder. The trajectories together with several model squaraine systems were studied to show the profound effects of disorder in the superstructure and disorder of the local monomer geometry on optical properties like absorption and exciton localization.

Conformational preferences of modified nucleobases in RNA aptamers and their effect on Förster resonant energy transfer.

Förster resonant energy transfer (FRET) can be utilized in the study of tertiary structures of RNA aptamers, which bind specific fluorophoric ligands to form a fluorogenic aptamer complex. By introducing the emissive nucleobase analog 4-cyanoindole into the fluorogenic Chili RNA aptamer a FRET pair was established. The interpretation of studies aiming to investigate those tertiary structures using FRET, however, relies on prior knowledge about conformational properties of the nucleobase, which govern exciton transfer capabilities.

HORTENSIA, a program package for the simulation of nonadiabatic autoionization dynamics in molecules.

We present a program package for the simulation of ultrafast vibration-induced autoionization dynamics in molecular anions in the manifold of the adiabatic anionic states and the discretized ionization continuum. This program, called HORTENSIA (Hopping Real-time Trajectories for Electron-ejection by Nonadiabatic Self-Ionization in Anions), is based on the nonadiabatic surface-hopping methodology, wherein nuclei are propagated as an ensemble along classical trajectories in the quantum-mechanical potential created by the electronic density of the molecular system. The electronic Schrödinger equation is numerically integrated along the trajectory, providing the time evolution of electronic state coefficients, from which switching probabilities into discrete electronic states are determined.

Chiroptical Properties of Planar Benzobisthiazole-Bridged Squaraine Dimers.

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.

Time-resolved photoelectron spectroscopy of 4-(dimethylamino)benzethyne - an experimental and computational study.

We investigated the excited-state dynamics of 4-(dimethylamino)benzethyne (4-DMABE) in a combined theoretical and experimental study using surface-hopping simulations and time-resolved ionisation experiments. The simulations predict a decay of the initially excited S state into the S state in only a few femtoseconds, inducing a subsequent partial twist of the dimethylamino group within ∼100 fs. This leads to drastically reduced Franck-Condon factors for the ionisation transition to the cationic ground state, thus inhibiting the effective ionisation of the molecule, which leads to a vanishing photoelectron signal on a similar timescale as observed in our time-resolved photoelectron spectra.

Ultrafast Ring Closure Reaction of Gaseous -Stilbene from S(ππ*).

-Stilbene (-St) is a well-known benchmark system for - photoisomerization. -St also produces 4a,4b-dihydrophenanthrene (DHP) in solution with a quantum yield of less than 0.19.

Long-range corrected fragment molecular orbital density functional tight-binding method for excited states in large molecular systems.

Herein, we present a new method to efficiently calculate electronically excited states in large molecular assemblies, consisting of hundreds of molecules. For this purpose, we combine the long-range corrected tight-binding density functional fragment molecular orbital method (FMO-LC-DFTB) with an excitonic Hamiltonian, which is constructed in the basis of locally excited and charge-transfer configuration state functions calculated for embedded monomers and dimers and accounts explicitly for the electronic coupling between all types of excitons. We first evaluate both the accuracy and efficiency of our fragmentation approach for molecular dimers and aggregates by comparing it with the full LC-TD-DFTB method.

Internal conversion rates from the extended thawed Gaussian approximation: Theory and validation.

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.

Quantum-classical dynamics of vibration-induced autoionization in molecules.

We present a novel method for the simulation of the vibration-induced autoionization dynamics in molecular anions in the framework of the quantum-classical surface hopping approach. Classical trajectories starting from quantum initial conditions are propagated on a quantum-mechanical potential energy surface while allowing for autoionization through transitions into discretized continuum states. These transitions are induced by the couplings between the electronic states of the bound anionic system and the electron-detached system composed of the neutral molecule and the free electron.

Stacking Is Favored over Hydrogen Bonding in Azaphenanthrene Dimers.

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.

(De)localization dynamics of molecular excitons: comparison of mixed quantum-classical and fully quantum treatments.

Molecular excitons play a central role in processes of solar energy conversion, both natural and artificial. It is therefore no wonder that numerous experimental and theoretical investigations in the last decade, employing state-of-the-art spectroscopic techniques and computational methods, have been driven by the common aim to unravel exciton dynamics in multichromophoric systems. Theoretically, exciton (de)localization and transfer dynamics are most often modelled using either mixed quantum-classical approaches (, trajectory surface hopping) or fully quantum mechanical treatments (either using model diabatic Hamiltonians or direct dynamics).

Transforming Dyes into Fluorophores: Exciton-Induced Emission with Chain-like Oligo-BODIPY Superstructures.

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.

Excimer formation dynamics in the isolated tetracene dimer.

The understanding of excimer formation and its interplay with the singlet-correlated triplet pair state (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 state and reveal a biexponential time dependence.

Real-time observation of photoionization-induced water migration dynamics in 4-methylformanilide-water by picosecond time-resolved infrared spectroscopy and molecular dynamics simulations.

A novel time-resolved pump-probe spectroscopic approach that enables to keep high resolution in both the time and energy domain, nanosecond excitation-picosecond ionization-picosecond infrared probe (ns-ps-ps TRIR) spectroscopy, has been applied to the -4-methylformanilide-water (4MetFA-W) cluster. Water migration dynamics from the CO to the NH binding site in a peptide linkage triggered by photoionization of 4MetFA-W is directly monitored by the ps time evolution of IR spectra, and the presence of an intermediate state is revealed. The time evolution is analyzed by rate equations based on a four-state model of the migration dynamics.

On the quantum and classical control of laser-driven isomerization in the Wigner representation.

We investigate the validity of the classical approximation to the numerically exact quantum dynamics for infrared laser-driven control of isomerization processes. To this end, we simulate the fully quantum mechanical dynamics both by wavepacket propagation in position space and by propagating the Wigner function in phase space employing a quantum-mechanical correction term. A systematic comparison is made with purely classical propagation of the Wigner function.

Ultrafast Ring-Opening Reaction of 1,3-Cyclohexadiene: Identification of Nonadiabatic Pathway via Doubly Excited State.

The photoinduced ring-opening reaction of 1,3-cyclohexadiene (CHD) to produce 1,3,5-hexatriene (HT) plays an essential role in the photobiological synthesis of vitamin D in the skin. This reaction follows the Woodward-Hoffmann rule, and C-C bond rupture via an electronically excited state occurs with conrotatory motion of the end CH groups. However, it is noted that the photoexcited S(π,π*) state of CHD is not electronically correlated with the ground state of HT, and the reaction must proceed via nonadiabatic transitions.

Ultrafast Resonance Energy Transfer in Ethylene-Bridged BODIPY Heterooligomers: From Frenkel to Förster Coupling Limit.

A series of distinct BODIPY heterooligomers (dyads, triads, and tetrads) comprising a variable number of typical 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.