Photophysics of a nucleic acid-protein crosslinking model strongly depends on solvation dynamics: an experimental and theoretical study.

We present a combined experimental and theoretical study of the photophysics of 5-benzyluracil (5BU) in methanol, which is a model system for interactions between nucleic acids and proteins. A molecular dynamics study of 5BU in solution through efficient DFT-based hybrid ab initio potentials revealed a remarkable conformational flexibility - allowing the population of two main conformers - as well as specific solute-solvent interactions, which both appear as relevant factors for the observed 5BU optical absorption properties. The simulated absorption spectrum, calculated on such an ensemble, enabled a molecular interpretation of the experimental UV-Vis lowest energy band, which is also involved in the induced photo-reactivity upon irradiation. In particular, the first two excited states (mainly involving the uracil moiety) both contribute to the 5BU lowest energy absorption. Moreover, as a key finding, the nature and brightness of such electronic transitions are strongly influenced by 5BU conformation and the microsolvation of its heteroatoms.

Evidence of Excited-State Vibrational Mode Governing the Photorelaxation of a Charge-Transfer Complex.

Modern, nonlinear, time-resolved spectroscopic techniques have opened new doors for investigating the intriguing but complex world of photoinduced ultrafast out-of-equilibrium phenomena and charge dynamics. The interaction between light and matter introduces an additional dimension, where the complex interplay between electronic and vibrational dynamics needs the most advanced theoretical-computational protocols to be fully understood on the molecular scale. In this study, we showcase the capabilities of ab initio molecular dynamics simulation integrated with a multiresolution wavelet protocol to carefully investigate the excited-state relaxation dynamics in a noncovalent complex involving tetramethylbenzene (TMB) and tetracyanoquinodimethane (TCNQ) undergoing charge transfer (CT) upon photoexcitation. Our protocol provides an accurate description that facilitates a direct comparison between transient vibrational analysis and time-resolved spectroscopic signals. This molecular level perspective enhances our understanding of photorelaxation processes confined in the adiabatic regime and offers an improved interpretation of vibrational spectra. Furthermore, it enables the quantification of anharmonic vibrational couplings between high- and low-frequency modes, specifically the TCNQ "rocking" and "bending" modes. Additionally, it identifies the primary vibrational mode that governs the adiabaticity between the ground state and the CT state. This comprehensive understanding of photorelaxation processes holds significant importance in the rational design and precise control of more efficient photovoltaic and sensor devices.

Tuning ultrafast time-evolution of photo-induced charge-transfer states: A real-time electronic dynamics study in substituted indenotetracene derivatives.

Photo-induced charge transfer (CT) states are pivotal in many technological and biological processes. A deeper knowledge of such states is mandatory for modeling the charge migration dynamics. Real-time time-dependent density functional theory (RT-TD-DFT) electronic dynamics simulations are employed to explicitly observe the electronic density time-evolution upon photo-excitation. Asymmetrically substituted indenotetracene molecules, given their potential application as n-type semiconductors in organic photovoltaic materials, are here investigated. Effects of substituents with different electron-donating characters are analyzed in terms of the overall electronic energy spacing and resulting ultrafast CT dynamics through linear response (LR-)TD-DFT and RT-TD-DFT based approaches. The combination of the computational techniques here employed provided direct access to the electronic density reorganization in time and to its spatial and rational representation in terms of molecular orbital occupation time evolution. Such results can be exploited to design peculiar directional charge dynamics, crucial when photoactive materials are used for light-harvesting applications.

Watching the Interplay between Photoinduced Ultrafast Charge Dynamics and Nuclear Vibrations.

Here is presented the ultrafast hole-electron dynamics of photoinduced metal to ligand charge-transfer (MLCT) states in a Ru(II) complex, [Ru(dcbpy)2(NCS)2]4- (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine), a photoactive molecule employed in dye sensitized solar cells. Via cutting-edge computational techniques, a tailored computational protocol is here presented and developed to provide a detailed analysis of the electronic manifold coupled with nuclear vibrations to better understand the nonradiative pathways and the resulting overall dye performances in light-harvesting processes (electron injection). Thus, the effects of different vibrational modes were investigated on both the electronic levels and charge transfer dynamics through a theoretical-computational approach. First, the linear response time-dependent density functional (LR-TDDFT) formalism was employed to characterize excitation energies and spacing among electronic levels (the electronic layouts). Then, to understand the ultrafast (femtosecond) charge dynamics on the molecular scale, we relied on the nonperturbative mean-field quantum electronic dynamics via real-time (RT-) TDDFT. Three vibrational modes were selected, representative for collective nuclear movements that can have a significant influence on the electronic structure: two involving NCS- ligands and one involving dcbpy ligands. As main results, we observed that such MLCT states, under vibrational distortions, are strongly affected and a faster interligand electron transfer mechanism is observed along with an increasing MLCT character of the adiabatic electronic states approaching closer in energy due to the vibrations. Such findings can help both in providing a molecular picture of multidimensional vibro-electronic spectroscopic techniques, used to characterize ultrafast coherent and noncoherent dynamics of complex systems, and to improve dye performances with particular attention to the study of energy or charge transport processes and vibronic couplings.

Electronic Structures and Spectroscopic Signatures of Noble-Gas-Doped Nanodiamonds.

Fluorescent nanodiamonds, that is, those containing optically active defects, have attracted interest for their ability to be used as qubits; for in vivo imaging; and as sensors for spin, stress, and temperature. One of the most commonly studied nanodiamond color centers is the nitrogen vacancy. However, there is strong interest in discovering other impurity centers that provide localized midband gap transitions. Noble gas atoms have garnered attention since they have been discovered within nanodiamonds produced through high-pressure-high-temperature laser-heated diamond anvil cell synthesis methods, where they are commonly used as hydrostatic pressure media. Noble gas atoms that exist in macrosized natural or synthetic diamonds have been shown to be able to form color centers. This research uses ab initio density functional theory and cluster models to systematically study the localized electronic structure for group VIII impurities of nanodiamond, including helium, neon, argon, krypton, and xenon. An in-depth examination of the interaction between the noble gas atom and diamond lattice has been carried out. The changes to the vibrational and UV/vis absorption spectra have been analyzed. It was determined that the energetically preferred geometry is dependent on the atom size. Most noble gas defects are stabilized within the nanodiamond lattice and exist in tetrahedral interstitial positions, except for the largest noble gas studied in this work, Xe, which was determined to prefer a substitutional configuration. Both Kr and Xe are expected to be able to manifest visible/near-IR optical responses when included in the diamond lattice.

An Expedited Route to Optical and Electronic Properties at Finite Temperature via Unsupervised Learning.

Electronic properties and absorption spectra are the grounds to investigate molecular electronic states and their interactions with the environment. Modeling and computations are required for the molecular understanding and design strategies of photo-active materials and sensors. However, the interpretation of such properties demands expensive computations and dealing with the interplay of electronic excited states with the conformational freedom of the chromophores in complex matrices (i.e., solvents, biomolecules, crystals) at finite temperature. Computational protocols combining time dependent density functional theory and ab initio molecular dynamics (MD) have become very powerful in this field, although they require still a large number of computations for a detailed reproduction of electronic properties, such as band shapes. Besides the ongoing research in more traditional computational chemistry fields, data analysis and machine learning methods have been increasingly employed as complementary approaches for efficient data exploration, prediction and model development, starting from the data resulting from MD simulations and electronic structure calculations. In this work, dataset reduction capabilities by unsupervised clustering techniques applied to MD trajectories are proposed and tested for the ab initio modeling of electronic absorption spectra of two challenging case studies: a non-covalent charge-transfer dimer and a ruthenium complex in solution at room temperature. The K-medoids clustering technique is applied and is proven to be able to reduce by ∼100 times the total cost of excited state calculations on an MD sampling with no loss in the accuracy and it also provides an easier understanding of the representative structures (medoids) to be analyzed on the molecular scale.

Understanding Charge Dynamics in Dense Electronic Manifolds in Complex Environments.

Photoinduced charge transfer (CT) excited states and their relaxation mechanisms can be highly interdependent on the environment effects and the consequent changes in the electronic density. Providing a molecular interpretation of the ultrafast (subpicosecond) interplay between initial photoexcited states in such dense electronic manifolds in condensed phase is crucial for improving and understanding such phenomena. Real-time time-dependent density functional theory is here the method of choice to observe the charge density, explicitly propagated in an ultrafast time domain, along with all time-dependent properties that can be easily extracted from it. A designed protocol of analysis for real-time electronic dynamics to be applied to time evolving electronic density related properties to characterize both in time and in space CT dynamics in complex systems is here introduced and validated, proposing easy to be read cross-correlation maps. As case studies to test such tools, we present the photoinduced charge-transfer electronic dynamics of 5-benzyluracil, a mimic of nucleic acid/protein interactions, and the metal-to-ligand charge-transfer electronic dynamics in water solution of [Ru(dcbpy)2(NCS)2]4-, dcbpy = (4,4'-dicarboxy-2,2'-bipyridine), or "N34-", a dye sensitizer for solar cells. Electrostatic and explicit ab initio treatment of solvent molecules have been compared in the latter case, revealing the importance of the accurate modeling of mutual solute-solvent polarization on CT kinetics. We observed that explicit quantum mechanical treatment of solvent slowed down the charge carriers mobilities with respect to the gas-phase. When all water molecules were modeled instead as simpler embedded point charges, the electronic dynamics appeared enhanced, with a reduced hole-electron distance and higher mean velocities due to the close fixed charges and an artificially increased polarization effect. Such analysis tools and the presented case studies can help to unveil the influence of the electronic manifold, as well as of the finite temperature-induced structural distortions and the environment on the ultrafast charge motions.

Nature of the Ultrafast Interligands Electron Transfers in Dye-Sensitized Solar Cells.

Charge-transfer dynamics and interligand electron transfer (ILET) phenomena play a pivotal role in dye-sensitizers, mostly represented by the Ru-based polypyridyl complexes, for TiO2 and ZnO-based solar cells. Starting from metal-to-ligand charge-transfer (MLCT) excited states, charge dynamics and ILET can influence the overall device efficiency. In this letter, we focus on N34- dye ( [Ru(dcbpy)2(NCS)2]4-, dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) to provide a first direct observation with high time resolution (<20 fs) of the ultrafast electron exchange between bpy-like ligands. ILET is observed in water solution after photoexcitation in the ∼400 nm MLCT band, and assessment of its ultrafast time-scale is here given through a real-time electronic dynamics simulation on the basis of state-of-the-art electronic structure methods. Indirect effects of water at finite temperature are also disentangled by investigating the system in a symmetric gas-phase structure. As main result, remarkably, the ILET mechanism appears to be based upon a purely electronic evolution among the dense, experimentally accessible, MLCT excited states manifold at ∼400 nm, which rules out nuclear-electronic couplings and proves further the importance of the dense electronic manifold in improving the efficiency of dye sensitizers in solar cell devices.

Electronic and Vibrational Manifold of Tetracyanoethylene-Chloronaphthalene Charge Transfer Complex in Solution: Insights from TD-DFT and Ab Initio Molecular Dynamics.

The interplay between light absorption and the molecular environment has a central role in the observed photophysics of a wide range of photoinduced chemical and biological phenomena. The understanding of the interplay between vibrational and electronic transitions is the focus of this work, since it can provide a rationale to tune the optical properties of charge transfer (CT) materials used for technological applications. A clear description of these processes poses a nontrivial challenge from both the theoretical and experimental points of view, where the main issue is how to accurately describe and probe drastic changes in the electronic structure and the ultrafast molecular relaxation and dynamics. In this work we focused on the intermolecular CT reaction that occurs upon photon absorption in a π-stacked model system in dichloromethane solution, in which the 1-chloronaphthalene (1ClN) acts as the electron donor and tetracyanoethylene (TCNE) is the electron acceptor. Density functional theory calculations have been carried out to characterize both the ground-state properties and more importantly the low-lying CT electronic transition, and excellent agreement with recently available experimental results [Mathies, R. A.; et al. J. Phys. Chem. A 2018, 122 (14), 3594] was obtained. The minima of the ground state and first singlet excited state have been accurately characterized in terms of spatial arrangements and vibrational Raman frequencies, and the CT natures of the first two low-lying electronic transitions in the absorption spectra have been addressed and clarified too. Finally, by modeling the possible coordination sites of the TCNE electron acceptor with respect to monovalent ions (Na+, K+) in an implicit solution of acetonitrile, we find that TCNE can accommodate a counterion in two different arrangements, parallel and orthogonal to the C═C axis, leading to the formation of a contact ion pair. The nature of the counterion and its relative position entail structural modifications of the TCNE radical anion, mainly the central C═C and C≡N bonds, compared to the isolated case. An important red shift of the C═C stretching frequency was observed when the counterion is orthogonal to the double bond, to a greater extent for Na+. On the contrary, in the second case, where the counterion ion lies along the internuclear C═C axis, we find that K+ polarizes the electron density of the double bond more, resulting in a greater red shift than with Na+.

Direct observation of the solvent organization and nuclear vibrations of [Ru(dcbpy)2(NCS)2]4-, [dcbpy = (4,4'-dicarboxy-2,2'-bipyridine)], via ab initio molecular dynamics.

Environmental effects can drastically influence the optical properties and photoreactivity of molecules, particularly in the presence of polar and/or protic solvents. In this work we investigate a negatively charged Ru(II) complex, [Ru(dcbpy)2(NCS)2]4- [dcbpy = (4,4'-dicarboxy-2,2'-bipyridine)], in water solution, since this system belongs to a broader class of transition-metal compounds undergoing upon photo-excitation rapid and complex charge transfer (CT) dynamics, which can be dictated by structural rearrangement and solvent environment. Ab initio molecular dynamics (AIMD) relying on a hybrid quantum/molecular mechanics scheme is used to probe the equilibrium microsolvation around the metal complex in terms of radial distribution functions of the main solvation sites and solvent effects on the overall equilibrium structure. Then, using our AIMD-based generalized normal mode approach, we investigate how the ligand vibrational spectroscopic features are affected by water solvation, also contributing to the interpretation of experimental Infra-Red spectra. Two solvation sites are found for the ligands: the sulfur and the oxygen sites can interact on average with ∼4 and ∼3 water molecules, respectively, where a stronger interaction of the oxygen sites is highlighted. On average an overall dynamic distortion of the C2 symmetric gas-phase structure was found to be induced by water solvation. Vibrational analysis reproduced experimental values for ligand symmetric and asymmetric stretchings, linking the observed shifts with respect to the gas-phase to a complex solvent distribution around the system. This is the groundwork for future excited-state nuclear and electronic dynamics to monitor non-equilibrium processes of CT excitation in complex environments, such as exciton migration in photovoltaic technologies.

Interference of Polydatin/Resveratrol in the ACE2:Spike Recognition during COVID-19 Infection. A Focus on Their Potential Mechanism of Action through Computational and Biochemical Assays.

In the search for new therapeutic strategies to contrast SARS-CoV-2, we here studied the interaction of polydatin (PD) and resveratrol (RESV)-two natural stilbene polyphenols with manifold, well known biological activities-with Spike, the viral protein essential for virus entry into host cells, and ACE2, the angiotensin-converting enzyme present on the surface of multiple cell types (including respiratory epithelial cells) which is the main host receptor for Spike binding. Molecular Docking simulations evidenced that both compounds can bind Spike, ACE2 and the ACE2:Spike complex with good affinity, although the interaction of PD appears stronger than that of RESV on all the investigated targets. Preliminary biochemical assays revealed a significant inhibitory activity of the ACE2:Spike recognition with a dose-response effect only in the case of PD.

Exploring the Franck-Condon region of a photoexcited charge transfer complex in solution to interpret femtosecond stimulated Raman spectroscopy: excited state electronic structure methods to unveil non-radiative pathways.

We present electronic structure methods to unveil the non-radiative pathways of photoinduced charge transfer (CT) reactions that play a main role in photophysics and light harvesting technologies. A prototypical π-stacked molecular complex consisting of an electron donor (1-chloronaphthalene, 1ClN) and an electron acceptor (tetracyanoethylene, TCNE) was investigated in dichloromethane solution for this purpose. The characterization of TCNE:π:1ClN in both its equilibrium ground and photoinduced low-lying CT electronic states was performed by using a reliable and accurate theoretical-computational methodology exploiting ab initio molecular dynamics simulations. The structural and vibrational time evolution of key vibrational modes is found to be in excellent agreement with femtosecond stimulated Raman spectroscopy experiments [R. A. Mathies et al., J. Phys. Chem. A, 2018, 122, 14, 3594], unveiling a correlation between vibrational fingerprints and electronic properties. The evaluation of nonadiabatic coupling matrix elements along generalized normal modes has made possible the interpretation on the molecular scale of the activation of nonradiative relaxation pathways towards the ground electronic state. In particular, two low frequency vibrational modes such as the out of plane bending and dimer breathing and the TCNE central C[double bond, length as m-dash]C stretching play a prominent role in relaxation phenomena from the electronic CT state to the ground state one.

A Not Obvious Correlation Between the Structure of Green Fluorescent Protein Chromophore Pocket and Hydrogen Bond Dynamics: A Choreography From ab initio Molecular Dynamics.

The Green Fluorescent Protein (GFP) is a widely studied chemical system both for its large amount of applications and the complexity of the excited state proton transfer responsible of the change in the protonation state of the chromophore. A detailed investigation on the structure of the chromophore environment and the influence of chromophore form (either neutral or anionic) on it is of crucial importance to understand how these factors could potentially influence the protein function. In this study, we perform a detailed computational investigation based on the analysis of ab-initio molecular dynamics simulations, to disentangle the main structural quantities determining the fine balance in the chromophore environment. We found that specific hydrogen bonds interactions directly involving the chromophore (or not), are correlated to quantities, such as the volume of the cavity in which the chromophore is embedded and that it is importantly affected by the chromophore protonation state. The cross-correlation analysis performed on some of these hydrogen bonds and the cavity volume, demonstrates a direct correlation among them and we also identified the ones specifically involved in this correlation. We also found that specific interactions among residues far in the space are correlated, demonstrating the complexity of the chromophore environment and that many structural quantities have to be taken into account to properly describe and understand the main factors tuning the active site of the protein. From an overall evaluation of the results obtained in this work, it is shown that the residues which a priori are perceived to be spectators play instead an important role in both influencing the chromophore environment (cavity volume) and its dynamics (cross-correlations among spatially distant residues).

Multiresolution continuous wavelet transform for studying coupled solute-solvent vibrations via ab initio molecular dynamics.

Vibrational analysis in solution and the theoretical determination of infrared and Raman spectra are of key importance in many fields of chemical interest. Vibrational band dynamics of molecules and their sensitivity to the environment can also be captured by these spectroscopies in their time dependent version. However, it is often difficult to provide an interpretation of the experimental data at the molecular scale, such as molecular mechanisms or the processes hidden behind them. In this work, we present a theoretical-computational protocol based on ab initio molecular dynamics simulations and a combination of normal-like (generalized) mode analysis of solute-solvent clusters with a wavelet transform, for the first time. The case study is the vibrational dynamics of N-methyl-acetamide (NMA) in water solution, a well-known model of hydration of peptides and proteins. Amide modes are typical bands of peptide and protein backbone, and their couplings with the environment are very challenging in terms of the accurate prediction of solvent induced intensity and frequency shifts. The contribution of water molecules surrounding NMA to the composition of generalized and time resolved modes is introduced in our vibrational analysis, showing unequivocally its influence on the amide mode spectra. It is also shown that such mode compositions need the inclusion of the first shell solvent molecules to be accurately described. The wavelet analysis is proven to be strongly recommended to follow the time evolution of the spectra, and to capture vibrational band couplings and frequency shifts over time, preserving at the same time a well-balanced time-frequency resolution. This peculiar feature also allows one to perform a combined structural-vibrational analysis, where the different strengths of hydrogen bond interactions can quantitatively affect the amide bands over time at finite temperature. The proposed method allows for the direct connection between vibrational modes and local structural changes, providing a link from the spectroscopic observable to the structure, in this case the peptide backbone, and its hydration layouts.

Ab-initio molecular dynamics and hybrid explicit-implicit solvation model for aqueous and nonaqueous solvents: GFP chromophore in water and methanol solution as case study.

Solute-solvent interactions are proxies for understanding how the electronic density of a chromophore interacts with the environment in a more exhaustive way. The subtle balance between polarization, electrostatic, and non-bonded interactions need to be accurately described to obtain good agreement between simulations and experiments. First principles approaches providing accurate configurational sampling through molecular dynamics may be a suitable choice to describe solvent effects on solute chemical-physical properties and spectroscopic features, such as optical absorption of dyes. In this context, accurate energy potentials, obtained by hybrid implicit/explicit solvation methods along with employing nonperiodic boundary conditions, are required to represent bulk solvent around a large solute-solvent cluster. In this work, a novel strategy to simulate methanol solutions is proposed combining ab initio molecular dynamics, a hybrid implicit/explicit flexible solvent model, nonperiodic boundary conditions, and time dependent density functional theory. As case study, the robustness of the proposed protocol has been gauged by investigating the microsolvation and electronic absorption of the anionic green fluorescent protein chromophore in methanol and aqueous solution. Satisfactory results are obtained, reproducing the microsolvation layout of the chromophore and, as a consequence, the experimental trends shown by the optical absorption in different solvents.

Carboxylate Anchors Act as Exciton Reporters in 1.3 nm Indium Phosphide Nanoclusters.

Developing interfacial probes of ligand-nanocluster interactions is crucial for understanding and tailoring the optoelectronic properties of these emerging nanomaterials. Using transient IR spectroscopy, we demonstrate that ligand vibrational modes of oleate-capped 1.3 nm InP nanoclusters report on the photogenerated exciton. The exciton induces an intensity change in the asymmetric carboxylate stretching mode by 57% while generating no appreciable shift in frequency. Thus, the observed difference signal is attributed to an exciton-induced change in the dipole magnitude of the asymmetric carboxylate stretching mode. Additionally, the transient IR data reveal that the infrared dipole change is dependent on the geometry of the ligand bound to the nanocluster. The experimental results are interpreted using TDDFT calculations, which identify how the spatial dependence of an exciton-induced electron density shift affects the vibrational motion of the carboxylate anchors. More broadly, this work demonstrates transient IR spectroscopy as a useful method for characterizing ligand-nanocluster coupling interactions.

Mapping Vibronic Couplings in a Solar Cell Dye with Polarization-Selective Two-Dimensional Electronic-Vibrational Spectroscopy.

This study uses polarization-selective two-dimensional electronic-vibrational (2D EV) spectroscopy to map intramolecular charge transfer in the well-known solar cell dye, [Ru(dcbpy)2(NCS)2]4- (N34-), dissolved in water. A static snapshot of the vibronic couplings present in aqueous N34- is reported. At least three different initially excited singlet metal-to-ligand charge-transfer (MLCT) states are observed to be coupled to vibrational modes probed in the lowest energy triplet MLCT state, emphasizing the role of vibronic coupling in intersystem crossing. Angles between electronic and vibrational transition dipole moments are extracted from spectrally isolated 2D EV peaks and compared with calculations to develop a microscopic description for how vibrations participate with 1MLCT states in charge transfer and intersystem crossing. These results suggest that 1MLCT states with significant electron density in the electron-donating plane formed by the Ru-(NCS)2 will participate strongly in charge transfer through these vibronically coupled degrees of freedom.

The mechanism of a green fluorescent protein proton shuttle unveiled in the time-resolved frequency domain by excited state ab initio dynamics.

We simulated an excited state proton transfer in green fluorescent protein by excited state ab initio dynamics, and examined the reaction mechanism in both the time and the frequency domain through a multi resolution wavelet analysis. This original approach allowed us, for the first time, to directly compare the trends of photoactivated vibrations to femtosecond stimulated Raman spectroscopy results, and to give an unequivocal interpretation of the role played by low frequency modes in promoting the reaction. We could attribute the main driving force of the reaction to an important photoinduced softening of the ring-ring orientational motion of the chromophore, thus permitting the tightening of the hydrogen bond network and the opening of the reaction pathway. We also found that both the chromophore (in terms of its inter-ring dihedral angle and phenolic C-O and imidazolinone C-N bond distances) and its pocket (in terms of the inter-molecular oxygen's dihedral angle of the chromophore pocket) relaxations are modulated by low frequency (about 120 cm-1) modes involving the oxygen atoms of the network. This is in agreement with the femtosecond Raman spectroscopy findings in the time-frequency domain. Moreover, the rate in proximity to the Franck Condon region involves a picosecond time scale, with a significant influence from fluctuations of nearby hydrogen bonded residues such as His148. This approach opens a new scenario with ab initio simulations as routinely used tools to understand photoreactivity and the results of advanced time resolved spectroscopy techniques.

Efficient Implementation of Variation after Projection Generalized Hartree-Fock.

Projected Hartree-Fock (PHF) theory can restore important symmetries to broken symmetry wave functions. Variation after projection (VAP) implementations make it possible to deliberately break and then restore a given symmetry by directly minimizing the projected energy expression. This technique can be applied to any symmetry that can be broken from relaxing constraints on single Slater determinant wave functions. For instance, generalized Hartree-Fock (GHF) wave functions are eigenfunctions of neither Sz nor S2. By relaxing these constraints, the wave function can explore a larger variational space and can reach lower energies than more constrained HF solutions. We have implemented spin-projected GHF (SGHF), which retains many of the advantages of breaking symmetry while also being a spin eigenfunction, with some notable improvements over previous implementations. Our new algorithm involves the formation of new intermediate matrices not previously discussed in the literature. Discretization of the necessary integration over the rotation group SO(3) is also accomplished much more efficiently using Lebedev grids. A novel scheme to incrementally build rotated Fock matrices is also introduced and compared with more standard approaches.

Ab Initio Excited-State Transient Raman Analysis.

Time-resolved Raman spectroscopy has proven useful for studying the formation of polarons in conjugated polymers, verifying the presence of reactive intermediates in photochemical reactions, investigating nonradiative transitions in the short lifetime of the photoexcited species, and resolving electron-phonon coupling strengths and exciton dissociation in crystalline materials. In this paper, we present an excited state transient Raman analysis protocol combining ab initio direct molecular dynamics, transient excited state Hessian, and excited state nonresonant Raman activities evaluations. Prototypical molecules are used as test cases, showing the evolution of the transient Raman signatures that follow electronic excitation. This protocol provides a direct route to assigning the vibrations implicated in the (photo)dynamics of several (photoactive) systems, complementary to the transient infrared analysis.