Norbornadiene-Quadricyclane Photoswitches with Enhanced Solar Spectrum Match.

Herein, we report monomeric and dimeric norbornadiene-quadricyclane molecular photoswitch systems intended for molecular solar thermal applications. A series of six new norbornadiene derivatives conjugated with benzothiadiazole as the acceptor unit and dithiafulvene as the donor unit were synthesized and fully characterized. The photoswitches were evaluated by experimentally and theoretically measuring optical absorption profiles and thermal conversion of quadricyclane to norbornadiene. Computational insight by density functional theory calculations at the M06-2X/def2-SVPD level of theory provided geometries, storage energies, UV-vis absorption spectra and HOMO-LUMO levels, that are used to describe the function of the molecular systems. The studied molecules exhibit absorption onset ranging from 416 nm to 595 nm due to a systemic change in their donor-acceptor character. This approach was advantageous due to the introduction of benzothiadiazole and the dimeric nature of molecular structures. The best-performing system has a half-life of 3 days.

A variational reformulation of molecular properties in electronic-structure theory.

Conventional quantum-mechanical calculations of molecular properties, such as dipole moments and electronic excitation energies, give errors that depend linearly on the error in the wave function. An exception is the electronic energy, whose error depends quadratically on the error in wave function. We here describe how all properties may be calculated with a quadratic error, by setting up a variational Lagrangian for the property of interest. Because the construction of the Lagrangian is less expensive than the calculation of the wave function, this approach substantially improves the accuracy of quantum-chemical calculations without increasing cost. As illustrated for excitation energies, this approach enables the accurate calculation of molecular properties for larger systems, with a short time-to-solution and in a manner well suited for modern computer architectures.

Pyrene Functionalized Norbornadiene-Quadricyclane Fluorescent Photoswitches: Characterization of their Spectral Properties and Application in Imaging of Amyloid Beta Plaques.

This study presents the synthesis and characterization of two fluorescent norbornadiene (NBD) photoswitches, each incorporating two conjugated pyrene units. Expanding on the limited repertoire of reported photoswitchable fluorescent NBDs, we explore their properties with a focus on applications in bioimaging of amyloid beta (Aß) plaques. While the fluorescence emission of the NBD decreases upon photoisomerization, aligning with what has been previously reported, for the first time we observed luminescence after irradiation of the quadricyclane (QC) isomer. We deduce how the observed emission is induced by photoisomerization to the excited state of the parent isomer (NBD) which is then the emitting species. Thorough characterizations including NMR, UV-Vis, fluorescence, X-ray structural analysis and density functional theory (DFT) calculations provide a comprehensive understanding of these systems. Notably, one NBD-QC system exhibits exceptional durability. Additionally, these molecules serve as effective fluorescent stains targeting Aß plaques in situ, with observed NBD/QC switching within the plaques. Molecular docking simulations explore NBD interactions with amyloid, unveiling novel binding modes. These insights mark a crucial advancement in the comprehension and design of future photochromic NBDs for bioimaging applications and beyond, emphasizing their potential in studying and addressing protein aggregates.

Dynamical Effects of Solvation on Norbornadiene/Quadricyclane Systems.

Molecules that can undergo reversible chemical transformations following the absorption of light, the so-called molecular photoswitches, have attracted increasing attention in technologies, such as solar energy storage. Here, the optical and thermochemical properties of the photoswitch are central to its applicability, and these properties are influenced significantly by solvation. We investigate the effects of solvation on two norbornadiene/quadricyclane photoswitches. Emphasis is put on the energy difference between the two isomers and the optical absorption as these are central to the application of the systems in solar energy storage. Using a combined classical molecular dynamics and quantum mechanical/molecular mechanical computational scheme, we showcase that the dynamic effects of solvation are important. In particular, it is found that standard implicit solvation models generally underestimate the energy difference between the two isomers and overestimate the strength of the absorption, while the explicit solvation spectra are also less red-shifted than those obtained using implicit solvation models. We also find that the absorption spectra of the two systems are strongly correlated with specific dihedral angles. Altogether, this highlights the importance of including the dynamic effects of solvation.

Cluster perturbation theory IX: Perturbation series for the coupled cluster singles and doubles ground state energy.

In this paper, we develop and analyze a number of perturbation series that target the coupled cluster singles and doubles (CCSD) ground state energy. We show how classical Møller-Plesset perturbation theory series can be restructured to target the CCSD energy based on a reference CCS calculation and how the corresponding cluster perturbation series differs from the classical Møller-Plesset perturbation series. Subsequently, we reformulate these series using the coupled cluster Lagrangian framework to obtain series, where fourth and fifth order energies are determined only using parameters through second order. To test the methods, we perform a series of test calculations on molecular photoswitches of both total energies and reaction energies. We find that the fifth order reaction energies are of CCSD quality and that they are of comparable accuracy to state-of-the-art approximations to the CCSD energy based on local pair natural orbitals. The advantage of the present approach over local correlation methods is the absence of user defined threshold parameters for neglecting or approximating contributions to the correlation energy. Fixed threshold parameters lead to discontinuous energy surfaces, although this effect is often small enough to be ignored, but the present approach has a differentiable energy that will facilitate derivation and implementation of gradients and higher derivatives. A further advantage is that the calculation of the perturbation correction is non-iterative and can, therefore, be calculated in parallel, leading to a short time-to-solution.

Tensor Hypercontraction of Cluster Perturbation Theory: Quartic Scaling Perturbation Series for the Coupled Cluster Singles and Doubles Ground-State Energies.

Even though cluster perturbation theory has been shown to be a robust noniterative alternative to coupled cluster theory, it is still plagued by high order polynomial computational scaling and the storage of higher order tensors. We present a proof-of-concept strategy for implementing a cluster perturbation theory ground-state energy series for the coupled cluster singles and doubles energy with N4 computational scaling using tensor hypercontraction (THC). The reduction in computational scaling by two orders is achieved by decomposing two electron repulsion integrals, doubles amplitudes and multipliers, as well as selected double intermediates to the THC format. Using the outlined strategy, we showcase that the THC pilot implementations retain numerical accuracy to within 1 kcal/mol relative to corresponding conventional and density fitting implementations, and we empirically verify the N4 scaling.

A Combined Quantum Mechanics and Molecular Mechanics Approach for Simulating the Optical Properties of DNA-Stabilized Silver Nanoclusters.

DNA-stabilized silver nanoclusters have emerged as an intriguing type of nanomaterial due to their unique optical and electronic properties, with potential applications in areas such as biosensing and imaging. The development of efficient methods for modeling these properties is paramount for furthering the understanding and utilization of these clusters. In this study, a hybrid quantum mechanical and molecular mechanical approach for modeling the optical properties of a DNA-templated silver nanocluster is evaluated. The influence of different parameters, including ligand fragmentation, damping, embedding potential, basis set, and density functional, is investigated. The results demonstrate that the most important parameter is the type of atomic properties used to represent the ligands, with isotropic dipole-dipole polarizabilities outperforming the rest. This underscores the importance of an appropriate representation of the ligands, particularly through the selection of the properties used to represent them. Moreover, the results are compared to experimental data, showing that the applied methodology is reliable and effective for the modeling of DNA-stabilized silver nanoclusters. These findings offer valuable insights that may guide future computational efforts to explore and harness the potential of these novel systems.

Extended Tetrathiafulvalenes with Fluoreno[3,2-b]fluorene and Diindeno[1,2-b : 1',2'-i]anthracene Cores.

In one-dimensional polycyclic aromatic hydrocarbons (PAHs) containing five- and six-membered rings fused together, one key question is whether the structures possess a quinoidal or aromatic diradical character. Here, we generate such PAHs by reversible oxidation of PAH-extended tetrathiafulvalenes (TTFs). Extended TTFs were thus prepared and studied for their geometrical properties (crystallography), redox properties, and UV/Vis/NIR/EPR characteristics as a function of charge state. The EPR measurements of radical cations showed unique features for each PAH-TTF. The dications, formally composed of fluoreno[3,2-b]fluorene and diindeno[1,2-b:1',2'-i]anthracene cores, were experimentally found to exhibit singlet ground states. For the latter, calculations reveal the closed shell, quinoid singlet state to be isoenergetic with the open shell singlet diradical. Each charge state exhibited unique optical properties with radical cations absorbing strongly in the NIR region with signatures from π-dimers for the large core. The experimental results were paralleled and supported by detailed computations, including spin density distribution calculations, EPR simulations, and nucleus independent chemical shift (NICS) xy scans.

Investigation of Solvent Effects on the Molecular Energy Storage and Optical Properties of Bicyclooctadiene/Tetracyclooctane Photoswitches.

In this paper, we investigate the effects of solvation on the solar energy storage properties of bicyclooctadiene/tetracyclooctane (BOD/TCO) photoswitches. The solvent effects on the thermochemical and optical properties are studied in cyclohexane, toluene, dichloromethane, ethanol, acetonitrile, and a vacuum using density functional theory and coupled cluster theory. Our results show that the energy storage capacity of the BOD/TCO system increases as the solvent polarity increases, and the change is more significant with an unsubstituted system. The energy storage capacity of the substituted system is not dependent on the polarity of the solvent. As the solvent polarity increases, the absorption peaks shift away from each other and the absorption intensities increase. Overall, the solvents improve the performance of the optical properties and the energy storage capacities of the BOD/TCO molecular solar thermal systems.

Solvent-Induced Symmetry Breaking of the Photoinduced Charge Transfer Dynamics in the Bridged Perylene Dimer.

The charge transfer dynamics of the bridged perylene dimer were investigated with the recently developed solvent coupling Redfield time propagation model. The results are compared with previous experimental findings to showcase the significance and applicability of the model. The charge transfer dynamics in vacuum showed that no breaking of the charge transfer direction symmetry occurred upon optical excitation, in perfect agreement with the experiment. Meanwhile, attractive solute-solvent interactions facilitated by the dipole moments of the polar solvents were observed to break the charge transfer direction symmetry. The conformational isomerism effect on the transfer dynamics manifested itself by promoting different transport channels upon solvation. Consequently, the solvent coupling Redfield time propagation model was indeed found to be able to quantitatively describe the charge transfer dynamics including exotic phenomena such as symmetry breaking of charge transfer direction.

Corrigendum: Coupled cluster theory on modern heterogeneous supercomputers.

[This corrects the article DOI: 10.3389/fchem.2023.1154526.].

The Effects of Solvent Dynamics on the Back Reaction of Solar-Thermal Energy Storage Systems.

We have investigated dynamic solvent effects on molecular solar-thermal energy storage systems using models describing the effects of frequency dependent viscosities and dielectric constants on chemical reaction rates. We have utilized the generalized Langevin model for understanding how the reactions are affected by the frequency dependent viscosities and dielectric constants. Our results show that the rate constants of the molecular solar-thermal energy storage systems depend strongly on the dielectric electric solvent properties and the frequency dependent viscosities of the solvents.

Computational investigation of photoswitch conjugates for molecular solar energy storage.

Solar energy conversion and storage are vital for combating climate change. Molecular solar thermal systems offer a promising solution, where energy is stored in molecular compounds. This study investigates dyad molecular photoswitches by combining bicyclooctadiene/tetracyclooctane and dihydroazulene/vinylheptafulvene systems with phenyl and cyano groups. Density functional theory calculations were employed to determine molecular properties and consider solvation effects in toluene and dichloromethane. The results show that the combined systems have a predicted storage energy of up to 206.14 kJ mol-1 and an absorption peak at 390.26 nm with appreciable intensity. These dyad photoswitches exhibit favorable properties for molecular solar thermal storage and other applications. A comparison with individual photoswitches reveals advantages and disadvantages. The most effective conjugate has a slightly lower storage density than an equal mixture of individual systems, but it demonstrates better absorption characteristics, with improved overlap with the solar spectrum and higher absorption intensity. These findings contribute to the understanding of dyad molecular photoswitches, showcasing their potential for advanced energy storage and conversion technologies.

Heterocyclic [9]Helicenes Exhibiting Bright Circularly Polarized Luminescence.

We describe a concise synthetic strategy for the preparation of heterocyclic [9]helicenes and a simple preparative-scale protocol for the optical resolution of the resulting M- and P-enantiomers. The helicenes were characterized by single-crystal X-ray diffraction along with a range of spectroscopic and computational techniques. A fluorescence quantum yield of up to 65 % was observed, and the chiroptical properties of both M- and P-helicenes revealed large dissymmetry factors. The circularly polarized luminescence brightness reaches up to 17 M-1 cm-1 , as measured experimentally and verified computationally, which makes this the highest circularly polarized luminescence brightness among heterocyclic helicenes. We describe how chiroptical properties (both circular dichroism and circularly polarized luminescence) can be described and predicted using quantum chemical calculations. The synthetic approach also reveals by-products that originate from internal oxidation reactions, presumably mediated by the close proximity of the π-surfaces in the helicene structure.

Searching the Chemical Space of Bicyclic Dienes for Molecular Solar Thermal Energy Storage Candidates.

Photoswitches are molecular systems that are chemically transformed subsequent to interaction with light and they find potential application in many new technologies. The design and discovery of photoswitch candidates require intricate molecular engineering of a range of properties to optimize a candidate to a specific applications, a task which can be tackled efficiently using quantum chemical screening procedures. In this paper, we perform a large scale screening of approximately half a million bicyclic diene photoswitches in the context of molecular solar thermal energy storage using ab initio quantum chemical methods. We further device an efficient strategy for scoring the systems based on their predicted solar energy conversion efficiency and elucidate potential pitfalls of this approach. Our search through the chemical space of bicyclic dienes reveals systems with unprecedented solar energy conversion efficiencies and storage densities that show promising design guidelines for next generation molecular solar thermal energy storage systems.

Coupled cluster theory on modern heterogeneous supercomputers.

This study examines the computational challenges in elucidating intricate chemical systems, particularly through ab-initio methodologies. This work highlights the Divide-Expand-Consolidate (DEC) approach for coupled cluster (CC) theory-a linear-scaling, massively parallel framework-as a viable solution. Detailed scrutiny of the DEC framework reveals its extensive applicability for large chemical systems, yet it also acknowledges inherent limitations. To mitigate these constraints, the cluster perturbation theory is presented as an effective remedy. Attention is then directed towards the CPS (D-3) model, explicitly derived from a CC singles parent and a doubles auxiliary excitation space, for computing excitation energies. The reviewed new algorithms for the CPS (D-3) method efficiently capitalize on multiple nodes and graphical processing units, expediting heavy tensor contractions. As a result, CPS (D-3) emerges as a scalable, rapid, and precise solution for computing molecular properties in large molecular systems, marking it an efficient contender to conventional CC models.

Elucidating the Mystery of DNA-Templating Effects on a Silver Nanocluster.

This presentation considers the effects that DNA-templating has on the optical properties of a 16-atom silver cluster. To accomplish this, hybrid quantum mechanical and molecular mechanical simulations of a Ag16-DNA complex have been carried out and compared with pure time-dependent density functional theory calculations of two Ag16 clusters in vacuum. The presented results show that the templating DNA polymers both red-shift the one-photon absorption of the silver cluster and increase its intensity. This occurs through a change in cluster shape prompted by the structural constraints of the DNA ligands combined with silver-DNA interactions. The overall charge of the cluster also contributes to the observed optical response, as oxidation of the cluster results in a simultaneous blue-shift of the one-photon absorption and a decrease in intensity. Additionally, the changes in shape and environment also lead to a blue-shift and enhancement of the two-photon absorption.

Indirect nuclear spin-spin couplings with third-order contributions added to the SOPPA method.

In this article, a modification of the second-order polarization propagator approximation (SOPPA) method is introduced and illustrated for the calculation of the indirect nuclear spin-spin couplings. The standard SOPPA method, although cheaper in terms of computational cost, offers less accurate results than the ones obtained with coupled cluster methods. A new method, named SOPPA+A3-3, was therefore developed by adding the terms of the third-order A matrix that rely on the second-order double amplitudes. The performance of this third-order contribution was studied using the coupled cluster singles and doubles method as a reference, calculating the spin-spin couplings of molecules of diverse sizes and compositions, and comparing them to the SOPPA method. The results show that inclusion of this third-order contribution gives more accurate results than the standard SOPPA method with a level of accuracy close to that of the coupled cluster method with only a small increase in the computational cost of the response calculation that dominates the computational cost for small- to medium-sized molecules. The implementation of the first contributions to the third-order polarization propagator approximation in the Dalton program, thus, already shows a significant change in these molecular properties over those obtained with the standard SOPPA method.

Massively parallel GPU enabled third-order cluster perturbation excitation energies for cost-effective large scale excitation energy calculations.

We present here a massively parallel implementation of the recently developed CPS(D-3) excitation energy model that is based on cluster perturbation theory. The new algorithm extends the one developed in Baudin et al. [J. Chem. Phys., 150, 134110 (2019)] to leverage multiple nodes and utilize graphical processing units for the acceleration of heavy tensor contractions. Furthermore, we show that the extended algorithm scales efficiently with increasing amounts of computational resources and that the developed code enables CPS(D-3) excitation energy calculations on large molecular systems with a low time-to-solution. More specifically, calculations on systems with over 100 atoms and 1000 basis functions are possible in a few hours of wall clock time. This establishes CPS(D-3) excitation energies as a computationally efficient alternative to those obtained from the coupled-cluster singles and doubles model.

Calculation of electric field gradients in Cd(II) model complexes of the CueR protein metal site.

With this work we first test various DFT functionals against CCSD(T) for calculation of EFGs at the position of Cd(II) in a very small model system, Cd(SCH3)2. Moreover, the available basis sets in ADF are tested in terms of basis set convergence, and the effect of including relativistic effects using the scalar relativistic and spin orbit ZORA Hamiltonians is explored. The results indicate that an error of up to around 10% on the calculated EFG may be expected using spin-orbit ZORA and the BHandHLYP functional with a locally dense basis set. Next, this method was applied to model systems of the CueR protein, aiming to interpret 111Ag-PAC spectroscopic data. Note that 111Ag decays to 111Cd on which the PAC data are recorded. Surprisingly, model systems truncated - as is often done - at the first C-C bond from the central Cd(II) are inadequate in size, and larger model systems must be employed to achieve reliable EFG calculations. The calculated EFGs agree well with experimental PAC data, and indicate that shortly after the nuclear decay the structure relaxes from linear two-coordinate AgS2 in the native protein, to a structure (or structures) where Cd(II) recruits additional ligands such as backbone carbonyl oxygens to achieve higher coordination number(s).