Excitonic Configuration Interaction: Going Beyond the Frenkel Exciton Model.

We present the excitonic configuration interaction (ECI) method─a fragment-based analogue of the CI method for electronic structure calculations of multichromophoric systems. It can also be viewed as a generalization of the exciton approach, with the following properties: (i) It constructs the effective Hamiltonian exclusively from monomer calculations. (ii) It employs the strong orthogonality assumption and is exact within McWeeny's group function theory, thus requiring only one-electron density matrices of the monomer states. (iii) It is agnostic of the monomer electronic structure method, allowing us to use/combine different methods. (iv) It includes an embedding point charge scheme (called excitonic Hartree-Fock, EHF) to improve the accuracy of the monomer states, but such that the effective full-system Hamiltonian is not explicitly dependent on the embedding. (v) It is systematically improvable, by expanding the set of monomer states and by including configurations where two or more monomers are excited (defining the ECIS, ECISD, etc., methods). The performance of ECI is assessed by computing the absorption spectrum of two exemplary multichromophoric systems, using CIS as the monomer electronic structure method. The accuracy of ECI significantly depends on the chosen embedding charges and the ECI expansion. The most accurate assessed combinations─ECIS or ECISD with EHF embedding─yield spectra that agree qualitatively and quantitatively with full-system direct calculations, with deviations of the excitation energies below 0.1 eV. We also show that ECISD based on CIS monomer calculations can predict states where two monomers are excited simultaneously (e.g., triplet-triplet double-local excitations) that are inaccessible in a full-system CIS calculation.

Resolving Photoinduced Femtosecond Three-Dimensional Solute-Solvent Dynamics through Surface Hopping Simulations.

Photoinduced dynamics in solution is governed by mutual solute-solvent interactions, which give rise to phenomena like solvatochromism, the Stokes shift, dual fluorescence, or charge transfer. Understanding these phenomena requires simulating the solute's photoinduced dynamics and simultaneously resolving the three-dimensional solvent distribution dynamics. If using trajectory surface hopping (TSH) to this aim, thousands of trajectories are required to adequately sample the time-dependent three-dimensional solvent distribution functions, and thus resolve the solvent dynamics with sub-Ångstrom and femtosecond accuracy and sufficiently low noise levels. Unfortunately, simulating thousands of trajectories with TSH in the framework of hybrid quantum mechanical/molecular mechanical (QM/MM) can be prohibitively expensive when employing ab initio electronic structure methods. To tackle this challenge, we recently introduced a computationally efficient approach that combines efficient linear vibronic coupling models with molecular mechanics (LVC/MM) via electrostatic embedding [Polonius et al., JCTC 2023, 19, 7171-7186]. This method provides solvent-embedded, nonadiabatically coupled potential energy surfaces while scaling similarly to MM force fields. Here, we employ TSH with LVC/MM to unravel the photoinduced dynamics of two small thiocarbonyl compounds solvated in water. We describe how to estimate the number of trajectories required to produce nearly noise-free three-dimensional solvent distribution functions and present an analysis based on approximately 10,000 trajectories propagated for 3 ps. In the electronic ground state, both molecules exhibit in-plane hydrogen bonds to the sulfur atom. Shortly after excitation, these bonds are broken and reform perpendicular to the molecular plane on timescales that differ by an order of magnitude due to steric effects. We also show that the solvent relaxation dynamics is coupled to the electronic dynamics, including intersystem crossing. These findings are relevant to advance the understanding of the coupled solute-solvent dynamics of solvated photoexcited molecules, e.g., biologically relevant thio-nucleobases.

Interplay between protonation and Jahn-Teller effects in a manganese vanadium cubane water oxidation catalyst.

Understanding the protonation behavior of metal-oxo water oxidation catalysts is essential to improve catalyst efficiency and long-term performance, as well as to tune their properties for specific applications. In this work, we explore the basicity and protonation effects of the highly active water oxidation catalyst [(Mn4O4) (V4O13) (OAc)3]3- using density functional theory. We computed the relative free energies of protonation in a systematic fashion for all symmetry-inequivalent O atoms, where the presence of multiple oxidation states from Mn4IV to Mn4III and a rich Jahn-Teller isomerism adds a significant amount of complexity. For high oxidation states, the compound behaves like some other polyoxometalates, showing protonation preferably at the terminal and µ2-bridging O atoms of the vanadate cap. However, upon reduction, eventually, the protonation preference switches to the cubane O atoms, mostly driven by a strong increase in basicity for O atoms located along the Jahn-Teller axes. Our work further evidences that protonation can potentially lead to several chemical transformations, like disproportionation and charge transfer to vanadium, dissociation of ligands, or the opening of the cubane structure. Our simulated UV/Vis absorption spectra additionally provide valuable insights about how the protonation of the catalyst could be tracked experimentally. Overall, our analysis highlights the complexity involved in the protonation of heterometallic polyoxometalate clusters.

Adsorption of 4-(N,N-Dimethylamino)-4'-nitrostilbene on an Amorphous Silica Glass Surface.

Stilbenes are a compelling class of organic photoswitches with a high degree of tunability that sensitively depend on their environment. In this study, we investigate the adsorption properties of 4-(N,N-dimethylamino)-4'-nitrostilbene (DANS), a push-pull stilbene, on amorphous silica glass. Plane-wave density functional theory (DFT) calculations are used to understand how the trans and cis isomers of DANS interact with the amorphous surface and which are the most preferred modes of adsorption. Our calculations revealed that the O-H···O hydrogen bonds between the nitro group and hydroxyl groups of the silica surface dominate the intramolecular interaction. In addition to hydrogen bonding, O-H···π interactions with the aromatic ring and double bond play a critical role in adsorption, whereas C-H···O interactions are present, but contribute little. Therefore, both isomers of DANS favor parallel orientations such that not only the functional groups but also the aromatic parts can strongly interact with the glass surface.

Excited-State Dynamics Simulations of a Light-Driven Molecular Motor in Solution.

Molecular motors, where light can be transformed into motion, are promising in the design of nanomechanical devices. For applications, however, finding relationships between molecular motion and the environment is important. Here, we report the study of excited-state dynamics of an overcrowded alkene in solution using a hybrid quantum mechanics/molecular mechanics (QM/MM) approach combined with excited-state molecular dynamics simulations. Using QM/MM surface-hopping trajectories, we calculated time-resolved emission and transient absorption spectra. These show the rise of a short-lived Franck-Condon state, followed by the formation of a dark state in the first 150 fs before the molecular motor relaxes to the ground state in about 1 ps. From the analysis of radial distribution functions, we infer that the orientation of the solvent with respect to the molecular motor in the electronic excited state is similar to that in the ground state during the photoisomerization.

LVC/MM: A Hybrid Linear Vibronic Coupling/Molecular Mechanics Model with Distributed Multipole-Based Electrostatic Embedding for Highly Efficient Surface Hopping Dynamics in Solution.

We present a theoretical framework for a hybrid linear vibronic coupling model electrostatically embedded into a molecular mechanics environment, termed the linear vibronic coupling/molecular mechanics (LVC/MM) method, for the surface hopping including arbitrary coupling (SHARC) molecular dynamics package. Electrostatic embedding is realized through the computation of interactions between environment point charges and distributed multipole expansions (DMEs, up to quadrupoles) that represent each electronic state and transition densities in the diabatic basis. The DME parameters are obtained through a restrained electrostatic potential (RESP) fit, which we extended to yield higher-order multipoles. We also implemented in SHARC a scheme for achieving roto-translational invariance of LVC models as well as a general quantum mechanics/molecular mechanics (QM/MM) interface, an OpenMM interface, and restraining potentials for simulating liquid droplets. Using thioformaldehyde in water as a test case, we demonstrate that LVC/MM can accurately reproduce the solvation structure and energetics of rigid solutes, with errors on the order of 1-2 kcal/mol compared to a BP86/MM reference. The implementation in SHARC is shown to be very efficient, enabling the simulation of trajectories on the nanosecond time scale in a matter of days.

Not the usual suspect - an unexpected organometallic product during the synthesis of cytotoxic platinum(II) complexes.

The reaction of (1R,2R)-(cyclohexane-1,2-diamine)dichloridoplatinum(II) with maleic acid unexpectedly resulted in the formation of an organometallic platinum(II) complex featuring a C,O-coordinating ligand. Additionally, a small series of close derivatives with increasing lipophilicity was synthesized. All complexes were fully characterized by multinuclear one- and two-dimensional (1H, 13C, 15N, and 195Pt) NMR spectroscopy, high resolution mass spectrometry, and in one case by X-ray diffraction. The lipophilicity and the impact on the DNA secondary structure as well as the cytotoxic properties in three human cancer cell lines (A549, SW480, and CH1/PA-1) were investigated. Unexpectedly, no clear-cut trend in cytotoxicity was observed with increasing lipophilicity. Also unexpectedly, the complexes showed only a low potential to inhibit cancer cell growth and no sign of interaction with DNA, in sharp contrast to the parent drug oxaliplatin, which seems to be caused by the low reactivity of the investigated compounds.

Role of Ultrafast Internal Conversion and Intersystem Crossing in the Nonadiabatic Relaxation Dynamics of ortho-Nitrobenzaldehyde.

ortho-Nitrobenzaldehyde (oNBA) is a well-known photoactivated acid and a prototypical photolabile nitro-aromatic compound. Despite extensive investigations, the ultrafast relaxation dynamics of oNBA is still not properly understood, especially concerning the role of the triplet states. In this work, we provide an in-depth picture of this dynamics by combining single- and multireference electronic structure methods with potential energy surface exploration and nonadiabatic dynamics simulations using the Surface Hopping including ARbitary Couplings (SHARC) approach. Our results reveal that the initial decay from the bright ππ* state to the S1 minimum is barrierless. It involves three changes in electronic structure from ππ* (ring) to nπ* (nitro group), to nπ* (aldehyde group), and then to another nπ* (nitro group). The decay of the ππ* takes 60-80 fs and can be tracked with time-resolved luminescence spectroscopy, where we predict for the first time a short-lived coherence of the luminescence energy with a 25 fs period. Intersystem crossing can occur already during the S4 → S1 deactivation cascade but also from S1, with a time constant of about 2.4 ps and such that first a triplet ππ* state localized on the nitro group is populated. The triplet population first evolves into an nπ* and then quickly undergoes hydrogen transfer to form a biradical intermediate, from where the ketene is eventually produced. The majority of the excited population decays from S1 through two conical intersections of equal utilization, a previously unreported one involving a scissoring motion of the nitro group that leads back to the oNBA ground state and the one involving hydrogen transfer that leads to the ketene intermediate.

Nonadiabatic Forward Flux Sampling for Excited-State Rare Events.

We present a rare event sampling scheme applicable to coupled electronic excited states. In particular, we extend the forward flux sampling (FFS) method for rare event sampling to a nonadiabatic version (NAFFS) that uses the trajectory surface hopping (TSH) method for nonadiabatic dynamics. NAFFS is applied to two dynamically relevant excited-state models that feature an avoided crossing and a conical intersection with tunable parameters. We investigate how nonadiabatic couplings, temperature, and reaction barriers affect transition rate constants in regimes that cannot be otherwise obtained with plain, traditional TSH. The comparison with reference brute-force TSH simulations for limiting cases of rareness shows that NAFFS can be several orders of magnitude cheaper than conventional TSH and thus represents a conceptually novel tool to extend excited-state dynamics to time scales that are able to capture rare nonadiabatic events.

Excited states of ortho-nitrobenzaldehyde as a challenging case for single- and multi-reference electronic structure theory.

We present a large set of vertical excitation calculations for the ortho-nitrobenzaldehyde (oNBA) molecule, which exhibits a very challenging excited-state electronic structure like other nitroaromatic compounds. The single-reference methods produce mostly consistent results up to about 5.5 eV. By contrast, the CAS second-order perturbation theory (CASPT2) results depend sensitively on the employed parameters. At the CAS self-consistent field level, the energies of the bright ππ * states are strongly overestimated while doubly excited states appear too low and mix with these ππ * states. This mixing hampers the CASPT2 step, leading to inconsistent results. Only by increasing the number of states in the state-averaging step to about 40-to cover all bright ππ * states embedded in the double excitations-and employing extended multistate CASPT2 could CASPT2 results consistent with experiment be obtained. We assign the four bands in the molecule's spectrum: The weakest band at 3.7 eV arises from the n NO 2 π * states, the second one at 4.4 eV from the ππ * ( L b ) state, the shoulder at 5.2 eV from the ππ * ( L a ) state, and the maximum at 5.7 eV from the ππ * ( B a / B b ) states. We also highlight the importance of modern wave function analysis techniques in elucidating the absorption spectrum of challenging molecules.

Nonadiabatic excited-state dynamics of ReCl(CO)3(bpy) in two different solvents.

We present a study of excited-states relaxation of the complex ReCl(CO)3(bpy) (bpy = 2,2-bipyridine) using a nonadiabatic TD-DFT dynamics on spin-mixed potential energy surfaces in explicit acetonitrile (ACN) and dimethylsulfoxide (DMSO) solutions up to 800 fs. ReCl(CO)3(bpy) belongs to a group of important photosensitizers which show ultrafast biexponential subpicosecond fluorescence decay kinetics. The choice of solvents was motivated by the different excited-state relaxation dynamics observed in subpicosecond time-resolved IR (TRIR) experiments. Simulations of intersystem crossing (ISC) showed the development of spin-mixed states in both solvents. Transformation of time-dependent populations of spin-mixed states enabled to monitor the temporal evolution of individual singlet and triplet states, fitting of bi-exponential decay kinetics, and simulating the time-resolved fluorescence spectra that show only minor differences between the two solvents. Analysis of structural relaxation and solvent reorganization employing time-resolved proximal distribution functions pointed to the factors influencing the fluorescence decay time constants. Nonadiabatic dynamics simulations of time-evolution of electronic, molecular, and solvent structures emerge as a powerful technique to interpret time-resolved spectroscopic data and ultrafast photochemical reactivity.

Ultrafast Intersystem Crossing Dynamics of 6-Selenoguanine in Water.

Rationalizing the photochemistry of nucleobases where an oxygen is replaced by a heavier atom is essential for applications that exploit near-unity triplet quantum yields. Herein, we report on the ultrafast excited-state deactivation mechanism of 6-selenoguanine (6SeGua) in water by combining nonadiabatic trajectory surface-hopping dynamics with an electrostatic embedding quantum mechanics/molecular mechanics (QM/MM) scheme. We find that the predominant relaxation mechanism after irradiation starts on the bright singlet S2 state that converts internally to the dark S1 state, from which the population is transferred to the triplet T2 state via intersystem crossing and finally to the lowest T1 state. This S2 → S1 → T2 → T1 deactivation pathway is similar to that observed for the lighter 6-thioguanine (6tGua) analogue, but counterintuitively, the T1 lifetime of the heavier 6SeGua is shorter than that of 6tGua. This fact is explained by the smaller activation barrier to reach the T1/S0 crossing point and the larger spin-orbit couplings of 6SeGua compared to 6tGua. From the dynamical simulations, we also calculate transient absorption spectra (TAS), which provide two time constants (τ1 = 131 fs and τ2 = 191 fs) that are in excellent agreement with the experimentally reported value (τexp = 130 ± 50 fs) (Farrel et al. J. Am. Chem. Soc. 2018, 140, 11214). Intersystem crossing itself is calculated to occur with a time scale of 452 ± 38 fs, highlighting that the TAS is the result of a complex average of signals coming from different nonradiative processes and not intersystem crossing alone.

Resolving Femtosecond Solvent Reorganization Dynamics in an Iron Complex by Nonadiabatic Dynamics Simulations.

The ultrafast dynamical response of solute-solvent interactions plays a key role in transition metal complexes, where charge transfer states are ubiquitous. Nonetheless, there exist very few excited-state simulations of transition metal complexes in solution. Here, we carry out a nonadiabatic dynamics study of the iron complex [Fe(CN)4(bpy)]2- (bpy = 2,2'-bipyridine) in explicit aqueous solution. Implicit solvation models were found inadequate for reproducing the strong solvatochromism in the absorption spectra. Instead, direct solute-solvent interactions, in the form of hydrogen bonds, are responsible for the large observed solvatochromic shift and the general dynamical behavior of the complex in water. The simulations reveal an overall intersystem crossing time scale of 0.21 ± 0.01 ps and a strong reliance of this process on nuclear motion. A charge transfer character analysis shows a branched decay mechanism from the initially excited singlet metal-to-ligand charge transfer (1MLCT) states to triplet states of 3MLCT and metal-centered (3MC) character. We also find that solvent reorganization after excitation is ultrafast, on the order of 50 fs around the cyanides and slower around the bpy ligand. In contrast, the nuclear vibrational dynamics, in the form of Fe-ligand bond changes, takes place on slightly longer time scales. We demonstrate that the surprisingly fast solvent reorganizing should be observable in time-resolved X-ray solution scattering experiments, as simulated signals show strong contributions from the solute-solvent scattering cross term. Altogether, the simulations paint a comprehensive picture of the coupled and concurrent electronic, nuclear, and solvent dynamics and interactions in the first hundreds of femtoseconds after excitation.

Jahn-Teller Effects in a Vanadate-Stabilized Manganese-Oxo Cubane Water Oxidation Catalyst.

Heuristic rules that allow identifying the preferred mixed-valence isomers and Jahn-Teller axis arrangements in the water oxidation catalyst [(Mn4 O4 )(V4 O13 )(OAc)3 ]n- and its activated form [(Mn4 O4 )(V4 O13 )(OAc)2 (H2 O)(OH)]n- are derived. These rules are based on computing all combinatorially possible mixed-valence isomers and Jahn-Teller axis arrangements of the MnIII atoms, and associate energetic costs with some structural features, like crossings of multiple Jahn-Teller axes, the location of these axes, or the involved ligands. It is found that the different oxidation states localize on different Mn centers, giving rise to clear Jahn-Teller distortions, unlike in previous crystallographic findings where an apparent valence delocalization was found. The low barriers that connect different Jahn-Teller axis arrangements suggest that the system quickly interconverts between them, leading to the observation of averaged bond lengths in the crystal structure. We conclude that the combination of cubane-vanadate bonds that are chemically inert, cubane-acetate/water bonds that can be activated through a Jahn-Teller axis, and low activation barriers for intramolecular rearrangement of the Jahn-Teller axes plays an essential role in the reactivity of this and probably related compounds.

Surface Hopping Dynamics on Vibronic Coupling Models.

The simulation of photoinduced non-adiabatic dynamics is of great relevance in many scientific disciplines, ranging from physics and materials science to chemistry and biology. Upon light irradiation, different relaxation processes take place in which electronic and nuclear motion are intimately coupled. These are best described by the time-dependent molecular Schrödinger equation, but its solution poses fundamental practical challenges to contemporary theoretical chemistry. Two widely used and complementary approaches to this problem are multiconfigurational time-dependent Hartree (MCTDH) and trajectory surface hopping (SH). MCTDH is an accurate fully quantum-mechanical technique but often is feasible only in reduced dimensionality, in combination with approximate vibronic coupling (VC) Hamiltonians, or both (i.e., reduced-dimensional VC potentials). In contrast, SH is a quantum-classical technique that neglects most nuclear quantum effects but allows nuclear dynamics in full dimensionality by calculating potential energy surfaces on the fly. If nuclear quantum effects do not play a central role and a linear VC (LVC) Hamiltonian is appropriate-e.g., for stiff molecules that generally keep their conformation in the excited state-then it seems advantageous to combine the efficient LVC and SH techniques. In this Account, we describe how surface hopping based on an LVC Hamiltonian (SH/LVC)-as recently implemented in the SHARC surface hopping package-can provide an economical and automated approach to simulate non-adiabatic dynamics. First, we illustrate the potential of SH/LVC in a number of showcases, including intersystem crossing in SO2, intra-Rydberg dynamics in acetone, and several photophysical studies on large transition-metal complexes, which would be much more demanding or impossible to perform with other methods. While all of the applications provide very useful insights into light-induced phenomena, they also hint at difficulties faced by the SH/LVC methodology that need to be addressed in the future. Second, we contend that the SH/LVC approach can be useful to benchmark SH itself. By the use of the same (LVC) potentials as MCTDH calculations have employed for decades and by relying on the efficiency of SH/LVC, it is possible to directly compare multiple SH test calculations with a MCTDH reference and ponder the accuracy of various correction algorithms behind the SH methodology, such as decoherence corrections or momentum rescaling schemes. Third, we demonstrate how the efficiency of SH/LVC can also be exploited to identify essential nuclear and electronic degrees of freedom to be employed in more accurate MCTDH calculations. Lastly, we show that SH/LVC is able to advance the development of SH protocols that can describe nuclear dynamics including explicit laser fields-a very challenging endeavor for trajectory-based schemes. To end, this Account compiles the typical costs of contemporary SH simulations, evidencing the great advantages of using parametrized potentials. The LVC model is a sleeping beauty that, kissed by SH, is fueling the field of excited-state molecular dynamics. We hope that this Account will stimulate future research in this direction, leveraging the advantages of the SH/VC schemes to larger extents and extending their applicability to uncharted territories.

Spectral Signatures of Oxidation States in a Manganese-Oxo Cubane Water Oxidation Catalyst.

We report IR and UV/Vis spectroscopic signatures that allow discriminating between the oxidation states of the manganese-based water oxidation catalyst [(Mn4 O4 )(V4 O13 )(OAc)3 ]3- . Simulated IR spectra show that V=O stretching vibrations in the 900-1000 cm-1 region shift consistently by about 20 cm-1 per oxidation equivalent. Multiple bands in the 1450-1550 cm-1 region also change systematically upon oxidation/reduction. The computed UV/Vis spectra predict that the spectral range above 350 nm is characteristic of the managanese-oxo cubane oxidation state, whereas transitions at higher energy are due to the vanadate ligand. The presence of absorption signals above 680 nm is indicative of the presence of MnIII atoms. Spectroelectrochemical measurements of the oxidation from [Mn 2 III Mn 2 IV ] to [Mn 4 IV ] showed that the change in oxidation state can indeed be tracked by both IR and UV/Vis spectroscopy.

On the population of triplet states of 2-seleno-thymine.

The population and depopulation mechanisms leading to the lowest-lying triplet states of 2-Se-Thymine were studied at the MS-CASPT2/cc-pVDZ level of theory. Several critical points on different potential energy hypersurfaces were optimized, including minima, conical intersections, and singlet-triplet crossings. The accessibility of all relevant regions on the potential energy hypersurfaces was investigated by means of minimum energy paths and linear interpolation in internal coordinates techniques. Our analysis indicates that, after the population of the bright S2 state in the Franck-Condon region, the first photochemical event is a barrierless evolution towards one of its two minima. After that, three viable photophysical deactivation paths can take place. In one of them, the population in the S2 state is transferred to the T2 state via intersystem crossing and subsequently to the T1 state by internal conversion. Alternatively, the S1 state could be accessed by internal conversion through two distinct conical intersections with S2 state followed by singlet-triplet crossing with the T2 state. The absence of a second minimum on the T1 state and a small energy barrier on pathway along the potential energy surface towards the ground state from the lowest triplet state are attributed as potential reasons to explain why the lifetime of the triplet state of 2-Se-Thymine might be reduced in comparison with its thio-analogue.

Excited-State Properties and Relaxation Pathways of Selenium-Substituted Guanine Nucleobase in Aqueous Solution and DNA Duplex.

The excited-state properties and relaxation mechanisms after light irradiation of 6-selenoguanine (6SeG) in water and in DNA have been investigated using a quantum mechanics/molecular mechanics (QM/MM) approach with the multistate complete active space second-order perturbation theory (MS-CASPT2) method. In both environments, the S1 1(nSeπ5*) and S2 1(πSeπ5*) states are predicted to be the spectroscopically dark and bright states, respectively. Two triplet states, T1 3(πSeπ5*) and T2 3(nSeπ5*), are found energetically below the S2 state. Extending the QM region to include the 6SeG-Cyt base pair slightly stabilizes the S2 state and destabilizes the S1, due to hydrogen-bonding interactions, but it does not affect the order of the states. The optimized minima, conical intersections, and singlet-triplet crossings are very similar in water and in DNA, so that the same general mechanism is found. Additionally, for each excited state geometry optimization in DNA, three kind of structures ("up", "down", and "central") are optimized which differ from each other by the orientation of the C═Se group with respect to the surrounding guanine and thymine nucleobases. After irradiation to the S2 state, 6SeG evolves to the S2 minimum, near to a S2/S1 conical intersection that allows for internal conversion to the S1 state. Linear interpolation in internal coordinates indicate that the "central" orientation is less favorable since extra energy is needed to surmount the high barrier in order to reach the S2/S1 conical intersection. From the S1 state, 6SeG can further decay to the T1 3(πSeπ5*) state via intersystem crossing, where it will be trapped due to the existence of a sizable energy barrier between the T1 minimum and the T1/S0 crossing point. Although this general S2 → T1 mechanism takes place in both media, the presence of DNA induces a steeper S2 potential energy surface, that it is expected to accelerate the S2 → S1 internal conversion.

Particle Swarm Contour Search Algorithm.

In this article, we present a new algorithm called Particle Swarm Contour Search (PSCS)-a Particle Swarm Optimisation inspired algorithm to find object contours in 2D environments. Currently, most contour-finding algorithms are based on image processing and require a complete overview of the search space in which the contour is to be found. However, for real-world applications this would require a complete knowledge about the search space, which may not be always feasible or possible. The proposed algorithm removes this requirement and is only based on the local information of the particles to accurately identify a contour. Particles search for the contour of an object and then traverse alongside using their known information about positions in- and out-side of the object. Our experiments show that the proposed PSCS algorithm can deliver comparable results as the state-of-the-art.

Excimer Intermediates en Route to Long-Lived Charge-Transfer States in Single-Stranded Adenine DNA as Revealed by Nonadiabatic Dynamics.

The ultrafast time evolution of a single-stranded adenine DNA is studied using a hybrid multiscale quantum mechanics/molecular mechanics (QM/MM) scheme coupled to nonadiabatic surface hopping dynamics. As a model, we use (dA)20 where a stacked adenine tetramer is treated quantum chemically. The dynamical simulations combined with on-the-fly quantitative wave function analysis evidence the nature of the long-lived electronically excited states formed upon absorption of UV light. After a rapid decrease of the initially excited excitons, relaxation to monomer-like states and excimers occurs within 100 fs. The former monomeric states then relax into additional excimer states en route to forming stabilized charge-transfer states on a longer timescale of hundreds of femtoseconds. The different electronic-state characters is reflected on the spatial separation between the adenines: excimers and charge-transfer states show a much smaller spatial separation than the monomer-like states and the initially formed excitons.