Explicit Modelling of Spectral Bandshapes by a Mixed Quantum-Classical Approach: Solvent Order and Temperature Effects in the Optical Spectra of Distryrylbenzene.

The absorption and emission spectral shapes of a flexible organic probe,  the distyrylbenzene (DSB) dye, are simulated accounting for the effect of different environments of increasing complexity, ranging from a homogeneous, low-molecular-weight solvent, to a long-chain alkane, and, eventually, a channel-forming organic matrix.  Each embedding is treated explicitly, adopting a mixed quantum-classical approach, the Adiabatic Molecular Dynamics -- generalized vertical Hessian (Ad-MD|gVH) model, which allows a direct simulation of the environment-induced constraining effects on the vibronic spectral shapes.  In such a theoretical framework, the stiff modes of the dye are described at a quantum level within the harmonic approximation, including Duschinsky mixing effects, while flexible degrees of freedom of the solute (e.g. torsions) and those of the solvent are treated classically by means of molecular dynamics sampling. Such a setup is shown to reproduce the distinct effects exerted by the different environments in varied thermodynamic conditions.  Besides allowing for a first-principles rationale on the supramolecular mechanism leading to the experimental spectral features, this result represents the first successful application of the Ad-MD|gVH method to complex embeddings and supports its potential application to other heterogeneous environments, such as for instance pigment-protein complexes or organic dyes adsorbed into metal-organic frameworks.

A Portrait of the Chromophore as a Young System-Quantum-Derived Force Field Unraveling Solvent Reorganization upon Optical Excitation of Cyclocurcumin Derivatives.

The study of fast non-equilibrium solvent relaxation in organic chromophores is still challenging for molecular modeling and simulation approaches, and is often overlooked, even in the case of non-adiabatic dynamics simulations. Yet, especially in the case of photoswitches, the interaction with the environment can strongly modulate the photophysical outcomes. To unravel such a delicate interplay, in the present contribution we resorted to a mixed quantum-classical approach, based on quantum mechanically derived force fields. The main task is to rationalize the solvent reorganization pathways in chromophores derived from cyclocurcumin, which are suitable for light-activated chemotherapy to destabilize cellular lipid membranes. The accurate and reliable decryption delivered by the quantum-derived force fields points to important differences in the solvent's reorganization, in terms of both structure and time scale evolution.

Dynamic effects on the nonlinear optical properties of donor acceptor stenhouse adducts: insights from combined MD + QM simulations.

The second-order nonlinear optical (NLO) responses of a donor-acceptor stenhouse adduct (DASA) are investigated by using a computational approach combining molecular dynamics simulations and density functional theory (DFT) calculations. Specific force fields for the open and closed photoswitching forms are first parameterized and validated according to the Joyce protocol, in order to finely reproduce the geometrical features and potential energy surfaces of both isomers in chloroform solution. Then, DFT calculations are performed on structural snapshots extracted at regular time steps of the MD trajectories to address the influence of the thermalized conformational dynamics on the NLO responses related to hyper-Rayleigh scattering (HRS) experiments. We show that accounting for the structural dynamics largely enhances the HRS hyperpolarizability (ßHRS) compared to DFT calculations considering solely equilibrium geometries, and greatly improves the agreement with experimental measurements. Furthermore, we show that the NLO responses of the NLO-active open form are correlated with the bond order alternation along the triene bridge connecting the donor and acceptor moieties, which is rationalized using simple essential state models.

Integrated Quantum-Classical Protocol for the Realistic Description of Solvated Multinuclear Mixed-Valence Transition-Metal Complexes and Their Solvatochromic Properties.

Linear cyanide-bridged polymetallic complexes, which undergo photoinduced metal-to-metal charge transfer, represent prototypical systems for studying long-range electron-transfer reactions and understanding the role played by specific solute-solvent interactions in modulating the excited-state dynamics. To tackle this problem, while achieving a statistically meaningful description of the solvent and of its relaxation, one needs a computational approach capable of handling large polynuclear transition-metal complexes, both in their ground and excited states, as well as the ability to follow their dynamics in several environments up to nanosecond time scales. Here, we present a mixed quantum classical approach, which combines large-scale molecular dynamics (MD) simulations based on an accurate quantum mechanically derived force field (QMD-FF) and self-consistent QMD polarized point charges, with IR and UV-vis spectral calculations to model the solvation dynamics and optical properties of a cyano-bridged trinuclear mixed-valence compound (trans-[(NC)5FeIII(µ-CN)RuII(pyridine)4(µ-NC)FeIII(CN)5]4-). We demonstrate the reliability of the QMD-FF/MD approach in sampling the solute conformational space and capturing the local solute-solvent interactions by comparing the results with higher-level quantum mechanics/molecular mechanics (QM/MM) MD reference data. The IR spectra calculated along the classical MD trajectories in different solvents correctly predict the red shift of the CN stretching band in the aprotic medium (acetonitrile) and the subtle differences measured in water and methanol, respectively. By explicitly including the solvent molecules around the cyanide ligands and calculating the thermal averaged absorption spectra using time-dependent density functional theory calculations within the Tamm-Dancoff approximation, the experimental solvatochromic shift is quantitatively reproduced going from water to methanol, while it is overestimated for acetonitrile. This discrepancy can likely be traced back to the lack of important dispersion interactions between the solvent cyano groups and the pyridine substituents in our micro solvation model. The proposed protocol is applied to the ground state in water, methanol, and acetonitrile and can be flexibly generalized to study excited-state nonequilibrium solvation dynamics.

Non-Phenomenological Description of the Time-Resolved Emission in Solution with Quantum-Classical Vibronic Approaches-Application to Coumarin C153 in Methanol.

We report a joint experimental and theoretical work on the steady-state spectroscopy and time-resolved emission of the coumarin C153 dye in methanol. The lowest energy excited state of this molecule is characterized by an intramolecular charge transfer thus leading to remarkable shifts of the time-resolved emission spectra, dictated by the methanol reorganization dynamics. We selected this system as a prototypical test case for the first application of a novel computational protocol aimed at the prediction of transient emission spectral shapes, including both vibronic and solvent effects, without applying any phenomenological broadening. It combines a recently developed quantum-classical approach, the adiabatic molecular dynamics generalized vertical Hessian method (Ad-MD|gVH), with nonequilibrium molecular dynamics simulations. For the steady-state spectra we show that the Ad-MD|gVH approach is able to reproduce quite accurately the spectral shapes and the Stokes shift, while a ∼0.15 eV error is found on the prediction of the solvent shift going from gas phase to methanol. The spectral shape of the time-resolved emission signals is, overall, well reproduced, although the simulated spectra are slightly too broad and asymmetric at low energies with respect to experiments. As far as the spectral shift is concerned, the calculated spectra from 4 ps to 100 ps are in excellent agreement with experiments, correctly predicting the end of the solvent reorganization after about 20 ps. On the other hand, before 4 ps solvent dynamics is predicted to be too fast in the simulations and, in the sub-ps timescale, the uncertainty due to the experimental time resolution (300 fs) makes the comparison less straightforward. Finally, analysis of the reorganization of the first solvation shell surrounding the excited solute, based on atomic radial distribution functions and orientational correlations, indicates a fast solvent response (≈100 fs) characterized by the strengthening of the carbonyl-methanol hydrogen bond interactions, followed by the solvent reorientation, occurring on the ps timescale, to maximize local dipolar interactions.

Unraveling the contributions to the spectral shape of flexible dyes in solution: insights on the absorption spectrum of an oxyluciferin analogue.

We present a computational investigation of the absorption spectrum in water of 5,5-spirocyclopropyl-oxyluciferin (5,5-CprOxyLH), an analogue of the emitter compound responsible for the bioluminescence in fireflies. Several factors participate in determining the 5,5-CprOxyLH's spectral shape: (i) the contribution of the four close-energy excited states, which show significant non-adiabatic couplings, (ii) the flexible molecular structure and (iii) the specific interactions established with the surrounding environment, which strongly couple the protic solvent dynamics with the dye's spectral response. To tackle the challenge to capture and dissect the role of all these effects we preliminarily investigate the role of non-adiabatic couplings with quantum dynamics simulations and a linear vibronic coupling model in the gas phase. Then, we account for both the molecular flexibility and solvent interactions by resorting to a mixed quantum classical protocol, named Adiabatic Molecular Dynamics generalized Vertical Gradient (Ad-MD|gVG), which is built on a method recently proposed by some of us. It is rooted in the partition between stiff degrees of freedom of the dye, accounted for at the vibronic level within the harmonic approximation, and flexible degrees of freedom of the solute (and of the solvent), described classically through a sampling based on Molecular Dynamics (MD). Ad-MD|gVG avoids spurious effects arising in the excited state Hessians due to non-adiabatic couplings, and can therefore be applied to account for the contributions of the first four excited states to the 5,5-CprOxyLH absorption spectrum. The final simulated spectrum is in very good agreement with the experiment, especially when the MD is driven by a refined quantum-mechanically derived force-field. More importantly, the origin of each separate contribution to the spectral shape is appropriately accounted for, paving the way to future applications of the method to more complex systems or alternative spectroscopies, as emission or circular dichroism.

Solvent effects on catechol's binding affinity: investigating the role of the intra-molecular hydrogen bond through a multi-level computational approach.

The subtle interplay between the inter-molecular interactions established by catechol with the surrounding solvent and the intra-molecular hydrogen bond (HB) characterizing its conformational dynamics is investigated through a multi-level computational approach. First, quantum mechanical (QM) calculations are employed to accurately characterize both large portions of the catechol's potential energy surface and the interaction energy with neighboring solvent molecules. The acquired information is thereafter exploited to develop a QM derived force-field (QMD-FF), in turn employed in molecular dynamics (MD) simulations based on classical mechanics. The reliability of the QMD-FF is further validated through a comparison with the outcomes of ab initio molecular dynamics, also purposely carried out in this work. In agreement with recent experimental findings, the MD results reveal remarkable differences in the conformational behavior of isolated and solvated catechol, as well as among the investigated solvents, namely water, acetonitrile or cyclohexane. The rather strong intramolecular HB, settled between the vicinal phenolic groups and maintained in the gas phase, loses stability when catechol is solvated in polar solvents, and is definitively lost in protic solvents such as water. In fact, the internal energy increase associated with the rotation of one hydroxyl group and the breaking of the internal HB is well compensated by the intermolecular HB network available when both phenolic hydrogens point toward the surrounding solvent. In such a case, catechol is stabilized in a chelating conformation, which in turn could be very effective in water removal and surface anchoring. Besides unraveling the role of the different contributors that govern catechol's conformational dynamics, the QMD-FF developed in this work could be in future employed to model larger catechol containing molecules, due to its accuracy to reliably model both internal flexibility and solvent effects, while exploiting MD computational benefits to include more complex players as for instance surfaces, ions or biomolecules.

Accurate Quantum-Mechanically Derived Force-Fields through a Fragment-Based Approach: Balancing Specificity and Transferability in the Prediction of Self-Assembly in Soft Matter.

The wide range of time/length scales covered by self-assembly in soft matter makes molecular dynamics (MD) the ideal candidate for simulating such a supramolecular phenomenon at an atomistic level. However, the reliability of MD outcomes heavily relies on the accuracy of the adopted force-field (FF). The spontaneous re-ordering in liquid crystalline materials stands as a clear example of such collective self-assembling processes, driven by a subtle and delicate balance between supramolecular interactions and single-molecule flexibility. General-purpose transferable FFs often dramatically fail to reproduce such complex phenomena, for example, the error on the transition temperatures being larger than 100 K. Conversely, quantum-mechanically derived force-fields (QMD-FFs), specifically tailored for the target system, were recently shown (J. Phys. Chem. Lett.2022,13, 243) to allow for the required accuracy as they not only well reproduced transition temperatures but also yielded a quantitative agreement with the experiment on a wealth of structural, dynamic, and thermodynamic properties. The main drawback of this strategy stands in the computational burden connected to the numerous quantum mechanical (QM) calculations usually required for a target-specific parameterization, which has undoubtedly hampered the routine application of QMD-FFs. In this work, we propose a fragment-based strategy to extend the applicability of QMD-FFs, in which the amount of QM calculations is significantly reduced, being a single-molecule-optimized geometry and its Hessian matrix the only QM information required. To validate this route, a new FF is assembled for a large mesogen, exploiting the parameters obtained for two smaller liquid crystalline molecules, in this and previous work. Lengthy MD simulations are carried out with the new transferred QMD-FF, observing again a spontaneous re-orientation in the correct range of temperatures, with good agreement with the available experimental measures. The present results strongly suggest that a partial transfer of QMD-FF parameters can be invoked without a significant loss of accuracy, thus paving the way to exploit the method's intrinsic predictive capabilities in the simulation of novel soft materials.

Flexible Superlubricity Unveiled in Sidewinding Motion of Individual Polymeric Chains.

A combination of low temperature atomic force microcopy and molecular dynamic simulations is used to demonstrate that soft designer molecules realize a sidewinding motion when dragged over a gold surface. Exploiting their longitudinal flexibility, pyrenylene chains are indeed able to lower diffusion energy barriers via on-surface directional locking and molecular strain. The resulting ultralow friction reaches values on the order of tens of pN reported so far only for rigid chains sliding on an incommensurate surface. Therefore, we demonstrate how molecular flexibility can be harnessed to realize complex nanomotion while retaining a superlubric character. This is in contrast with the paradigm guiding the design of most superlubric nanocontacts (mismatched rigid contacting surfaces).

Complexes of Alkaline and Ammonium Cations with Dopamine and Eumelanin Precursors: Dissecting the Role of Noncovalent Cation-π and Cation-Lone Pair (σ-Type) Interactions.

Cation-π interactions and their possible competition with other noncovalent interactions (NCI) might play a key role in both dopamine- and eumelanin-based bioinspired materials. In this contribution, to unravel the delicate interplay between cation-π interactions and other possible competing forces, the configurational space of noncovalent complexes formed by dopamine or eumelanin precursors (o-benzoquinone, DHI and a semiquinone dimer) and three different cations (Na+, K+, and NH4+) is sampled by means of accurate ab initio calculations. To this end, we resort to the mp2mod method, recently validated by us for benzene-, phenol-, and catechol-cation complexes, whose computational convenience allows for an extensive exploration of the cation-molecule interaction energy surface, by sampling a total of more than 104 arrangements. The mp2mod interaction energy landscapes reveal that, besides the expected cation-π driven arrangements, for all considered molecule-cation pairs the most stable complexes are found when the cation lies within the plane containing the six-membered ring, thus maximizing the σ-type interaction with the oxygen's lone pairs. Due to the loss of aromaticity, the σ-type/cation-π strength ratio is remarkably large in o-benzoquinone, where cation-π complexes seem unlikely to be formed. The above features are shared among all considered cations but are significantly larger when considering the smaller Na+. Besides delivering a deeper insight onto the NCI network established by the considered precursors in the presence of ions, the present results can serve as a reference database to validate or refine lower level methods, as, for instance, the force fields employed in classical simulations.

How the Interplay among Conformational Disorder, Solvation, Local, and Charge-Transfer Excitations Affects the Absorption Spectrum and Photoinduced Dynamics of Perylene Diimide Dimers: A Molecular Dynamics/Quantum Vibronic Approach.

In this contribution we present a mixed quantum-classical dynamical approach for the computation of vibronic absorption spectra of molecular aggregates and their nonadiabatic dynamics, taking into account the coupling between local excitations (LE) and charge-transfer (CT) states. The approach is based on an adiabatic (Ad) separation between the soft degrees of freedom (DoFs) of the system and the stiff vibrations, which are described by the quantum dynamics (QD) of wave packets (WPs) moving on the coupled potential energy surfaces (PESs) of the LE and CT states. These PESs are described with a linear vibronic coupling (LVC) Hamiltonian, parameterized by an overlap-based diabatization on the grounds of time-dependent density functional theory computations. The WPs time evolution is computed with the multiconfiguration time-dependent Hartree method, using effective modes defined through a hierarchical representation of the LVC Hamiltonian. The soft DoFs are sampled with classical molecular dynamics (MD), and the coupling between the slow and fast DoFs is included by recomputing the key parameters of the LVC Hamiltonians, specifically for each MD configuration. This method, named Ad-MD|gLVC, is applied to a perylene diimide (PDI) dimer in acetonitrile and water solutions, and it is shown to accurately reproduce the change in the vibronic features of the absorption spectrum upon aggregation. Moreover, the microscopic insight offered by the MD trajectories allows for a detailed understanding of the role played by the fluctuation of the aggregate structure on the shape of the vibronic spectrum and on the population of LE and CT states. The nonadiabatic QD predicts an extremely fast (∼50 fs) energy transfer between the two LEs. CT states have only a moderate effect on the absorption spectrum, despite the fact that after photoexcitation they are shown to acquire a fast and non-negligible population, highlighting their relevance in dictating the charge separation and transport in PDI-based optical devices.

Predicting Spontaneous Orientational Self-Assembly: In Silico Design of Materials with Quantum Mechanically Derived Force Fields.

De novo design of self-assembled materials hinges upon our ability to relate macroscopic properties to individual building blocks, thus characterizing in such supramolecular architectures a wide range of observables at varied time/length scales. This work demonstrates that quantum mechanical derived force fields (QMD-FFs) do satisfy this requisite and, most importantly, do so in a predictive manner. To this end, a specific FF, built solely based on the knowledge of the target molecular structure, is employed to reproduce the spontaneous transition to an ordered liquid crystal phase. The simulations deliver a multiscale portrait of such self-assembly processes, where conformational changes within the individual building blocks are intertwined with a 200 ns ensemble reorganization. The extensive characterization provided not only is in quantitative agreement with the experiment but also connects the time/length scales at which it was performed. Realizing QMD-FF predictive power and unmatched accuracy stands as an important leap forward for the bottom-up design of advanced supramolecular materials.

Automated Parameterization of Quantum Mechanically Derived Force Fields for Soft Materials and Complex Fluids: Development and Validation.

The reliability of molecular dynamics (MD) simulations in predicting macroscopic properties of complex fluids and soft materials, such as liquid crystals, colloidal suspensions, or polymers, relies on the accuracy of the adopted force field (FF). We present an automated protocol to derive specific and accurate FFs, fully based on ab initio quantum mechanical (QM) data. The integration of the Joyce and Picky procedures, recently proposed by our group to provide an accurate description of simple liquids, is here extended to larger molecules, capable of exhibiting more complex fluid phases. While the standard Joyce protocol is employed to parameterize the intramolecular FF term, a new automated procedure is here proposed to handle the computational cost of the QM calculations required for the parameterization of the intermolecular FF term. The latter is thus obtained by integrating the old Picky procedure with a fragmentation reconstruction method (FRM) that allows for a reliable, yet computationally feasible sampling of the intermolecular energy surface at the QM level. The whole FF parameterization protocol is tested on a benchmark liquid crystal, and the performances of the resulting quantum mechanically derived (QMD) FF were compared with those delivered by a general-purpose, transferable one, and by the third, "hybrid" FF, where only the bonded terms were refined against QM data. Lengthy atomistic MD simulations are carried out with each FF on extended 5CB systems in both isotropic and nematic phases, eventually validating the proposed protocol by comparing the resulting macroscopic properties with other computational models and with experiments. The QMD-FF yields the best performances, reproducing both phases in the correct range of temperatures and well describing their structure, dynamics, and thermodynamic properties, thus providing a clear protocol that may be explored to predict such properties on other complex fluids or soft materials.

The Role of Non-Covalent Interactions on Cluster Formation: Pentamer, Hexamers and Heptamer of Difluoromethane.

The role of non-covalent interactions (NCIs) has broadened with the inclusion of new types of interactions and a plethora of weak donor/acceptor partners. This work illustrates the potential of chirped-pulse Fourier transform microwave technique, which has revolutionized the field of rotational spectroscopy. In particular, it has been exploited to reveal the role of NCIs' in the molecular self-aggregation of difluoromethane where a pentamer, two hexamers and a heptamer were detected. The development of a new automated assignment program and a sophisticated computational screening protocol was essential for identifying the homoclusters in conditions of spectral congestion. The major role of dispersion forces leads to less directional interactions and more distorted structures than those found in polar clusters, although a detailed analysis demonstrates that the dominant interaction energy is the pairwise interaction. The tetramer cluster is identified as a structural unit in larger clusters, representing the maximum expression of bond between dimers.

The phenoxyl group-modulated interplay of cation-π and σ-type interactions in the alkali metal series.

The interaction potential energy surfaces (IPESs) of four alkaline metal cations (Na+, K+, Rb+ and Cs+) complexed with phenol and catechol were explored by accurate ab initio calculations to investigate the interplay of different noncovalent interactions and their behavior along the alkali metal series and upon -OH substitution. Selected one-dimensional interaction energy curves revealed two different minimum energy configurations for all phenol- and catechol-metal complexes, characterized either by cation-π or σ-type interactions. For each investigated complex several two-dimensional IPES maps were also computed, exploiting the computational advantages of the MP2mod approach. The size of the alkali cation was found to play a similar role in modulating both kinds of complexes, as the interaction strength always decreases along the metal series, from Na+ to Cs+. Conversely, the number of hydroxyl substituents markedly affected cation-π complexes vs. σ-type ones. As a most relevant finding, in catechol-metal complexes the strength of cation-π interactions is around half that of the σ-type ones. It is argued that the combined effect of cation dimensions and hydroxyl substitution in catechol-Na+ complexes makes σ-type configurations remarkably more stable and easily accessible than cation-π ones. Besides shedding new light on the origin of biological phenomena connected with underwater adhesion, the quantum mechanical interaction energy database provided herein may offer a useful reference for tuning accurate force fields, suitable for molecular dynamics simulations, where environmental effects might be also taken into account.

Accounting for Vibronic Features through a Mixed Quantum-Classical Scheme: Structure, Dynamics, and Absorption Spectra of a Perylene Diimide Dye in Solution.

The optical absorption spectrum of a perylene diimide (PDI) dye in acetonitrile solution is simulated using the recently developed (J. Chem. Theory Comput. 2020, 16, 1215-1231) Ad-MD|gVH method. This mixed quantum-classical (MQC) approach is based on an adiabatic (Ad) separation of soft(classical)/stiff(quantum) nuclear degrees of freedom and expresses the spectrum as a conformational average (over the soft coordinates) of vibronic spectra (for the stiff coordinates) obtained through the generalized vertical Hessian (gVH) vibronic approach. The average is performed over snapshots extracted from classical molecular dynamics (MD) runs, performed with a specifically parameterized quantum-mechanically derived force field (QMD-FF). A comprehensive assessment of the reliability of different approaches, designed to reproduce spectral shapes of flexible molecules, is here presented. First, the differences in the sampled configurational space and their consequences on the prediction of the absorption spectra are evaluated by comparing the results obtained by means of the specific QMD-FF and of a general-purpose transferable FF with those of a reference ab initio MD (AIMD) in the gas phase, in both a purely classical scheme (ensemble average) and in the Ad-MD|gVH framework. Next, classical ensemble average and MQC predictions are also obtained for the PDI dynamics in solution and compared with the results of a ″static″ approach, based on vibronic calculations carried out on a single optimized perylene diimide structure. In the classical ensemble average approach, the remarkably different samplings obtained with the two FFs lead to sizeable changes in both position and intensity of the predicted spectra, with the one computed along the QMD-FF trajectory closely matching its AIMD counterpart. Conversely, at the Ad-MD|gVH level of theory, the different samplings deliver very similar vibronic spectra, indicating that the error found in the absorption spectra obtained with the general-purpose FF mainly concerns the stiff modes. In fact, it can be effectively corrected by the quadratic extrapolation performed by gVH to locate the minima of the ground- and excited-state potential energy surfaces along such coordinates. Furthermore, in the perspective of studying the self-assembling process of PDI dyes and the vibronic spectra of large-size aggregates, the use of a molecule-specific QMD-FF also appears mandatory, considering the significant errors found in the GAFF trajectory in the flexible lateral chain populations, which dictate the supramolecular aggregation properties.

Automated parameterization of quantum-mechanically derived force-fields including explicit sigma holes: A pathway to energetic and structural features of halogen bonds in gas and condensed phase.

In classical molecular dynamics, general purpose atomistic force-fields (FFs) often deliver inaccurate results when dealing with halogen bonds (XBs), notwithstanding their crucial role in many fields of science, ranging from material design to drug development. Given the large dimensions of the systems of interest, it would be therefore desirable to increase the FF accuracy maintaining the simplicity of the standard Lennard-Jones (LJ) plus point charge description to avoid an excessive computational cost. A simple yet effective strategy consists in introducing a number of virtual sites able to mimic the so-called "explicit σ-hole." In this work, we present an automated FF parameterization strategy based on a global optimization of both LJ and charge parameters with respect to accurate quantum mechanical data, purposely computed for the system under investigation. As a test case, we report on two homologue series, characterized either by weak or strong XBs, namely, the di-halogenated methanes and the mono-, di-, and tri-substituted acetonitriles, taking into consideration Cl, Br, and I substituents. The resulting quantum mechanically derived FFs are validated for each compound in the gas and in the condensed phase by comparing them to general purpose and specific FFs without virtual sites and to highly accurate reference quantum mechanical data. The results strongly support the adoption of the specific FFs with virtual sites, which overcome the other investigated models in representing both gas phase energetics and the structural patterns of the liquid phase structure related to the presence of XBs.

Iron's Wake: The Performance of Quantum Mechanical-Derived Versus General-Purpose Force Fields Tested on a Luminescent Iron Complex.

Recently synthetized iron complexes have achieved long-lived excited states and stabilities which are comparable, or even superior, to their ruthenium analogues, thus representing an eco-friendly and cheaper alternative to those materials based on rare metals. Most of computational tools which could help unravel the origin of this large efficiency rely on ab-initio methods which are not able, however, to capture the nanosecond time scale underlying these photophysical processes and the influence of their realistic environment. Therefore, it exists an urgent need of developing new low-cost, but still accurate enough, computational methodologies capable to deal with the steady-state and transient spectroscopy of transition metal complexes in solution. Following this idea, here we focus on the comparison between general-purpose transferable force-fields (FFs), directly available from existing databases, and specific quantum mechanical derived FFs (QMD-FFs), obtained in this work through the Joyce procedure. We have chosen a recently reported FeIII complex with nanosecond excited-state lifetime as a representative case. Our molecular dynamics (MD) simulations demonstrated that the QMD-FF nicely reproduces the structure and the dynamics of the complex and its chemical environment within the same precision as higher cost QM methods, whereas general-purpose FFs failed in this purpose. Although in this particular case the chemical environment plays a minor role on the photo physics of this system, these results highlight the potential of QMD-FFs to rationalize photophysical phenomena provided an accurate QM method to derive its parameters is chosen.

Benchmarking Cation-π Interactions: Assessment of Density Functional Theory and Möller-Plesset Second-Order Perturbation Theory Calculations with Optimized Basis Sets (mp2mod) for Complexes of Benzene, Phenol, and Catechol with Na+, K+, Rb+, and Cs.

The reliability of several density functional theory (DFT) functionals and of the Möller-Plesset second-order perturbation theory calculations with modified basis sets (mp2mod) approach in describing cation-π interactions is systematically investigated by benchmarking their performances with respect to high quality reference CCSD(T) calculations of the binding energies between alkaline cations of varying radius (Na+, K+, Rb+, and Cs+) and three aromatic species (benzene, phenol, and catechol). For this class of noncovalent interaction, mp2mod delivers, on average, results in very good agreement with the reference CCSD(T) data, yet at a very small computational cost, exploiting the reduced dimensions of the modified basis set. Conversely, the tested DFT functionals show a more erratic behavior, with different performances depending on both the investigated system and the combination of the employed functional and basis set. The mp2mod computational convenience is further exploited to extensively sample two-dimensional interaction energy surfaces of all investigated cation-π systems, which allow for a deeper insight on the effect of the increasing number of hydroxyl substituents, revealing the insurgence, upon substitution, of alternative minima, evident in particular for the smaller cations. The present results strongly support for further applications of the mp2mod method to study a larger variety of aromatic/metal cation species, relevant both in biological processes and in technological applications.

Adiabatic-Molecular Dynamics Generalized Vertical Hessian Approach: A Mixed Quantum Classical Method To Compute Electronic Spectra of Flexible Molecules in the Condensed Phase.

We present a general mixed quantum classical method that couples classical molecular dynamics (MD) and vibronic models to compute the shape of electronic spectra of flexible molecules in the condensed phase without, in principle, any phenomenological broadening. It is based on a partition of the nuclear motions of the solute + solvent system in "soft" and "stiff" vibrational modes and an adiabatic hypothesis that assumes that stiff modes are much faster than soft ones. In this framework, the spectrum is rigorously expressed as a conformational integral of quantum vibronic spectra along the stiff coordinates only. Soft modes enter at the classical level through the conformational distribution that is sampled with classical MD runs. In each configuration, reduced-dimensionality quadratic Hamiltonians are built in the space of the stiff coordinates only, thanks to a generalization of the Vertical Hessian harmonic model and an iterative application of projectors in internal coordinates to remove soft modes. Quantum vibronic spectra, specific for each sampled configuration of the soft coordinates, are then computed at the desired temperature with efficient time-dependent techniques, and the global spectrum simply arises from their average. For consistency of the whole procedure, classical MD runs are performed with quantum-mechanically derived force fields, parameterized at the same level of theory selected for generating the quadratic Hamiltonians along the stiff coordinates. Application to N-methyl-6-oxyquinolinium betaine in water, dithiophene in ethanol, and cyanidine in water is presented to show the performance of the method.