Antioxidative Triplet Excitation Energy Transfer in Bacterial Reaction Center Using a Screened Range Separated Hybrid Functional.

Excess energy absorbed by photosystems (PSs) can result in photoinduced oxidative damage. Transfer of such energy within the core pigments of the reaction center in the form of triplet excitation is important in regulating and preserving the functionality of PSs. In the bacterial reaction center (BRC), the special pair (P) is understood to act as the electron donor in a photoinduced charge transfer process, triggering the charge separation process through the photoactive branch A pigments that experience a higher polarizing environment. At this work, triplet excitation energy transfer (TEET) in BRC is studied using a computational perspective to gain insights into the roles of the dielectric environment and interpigment orientations. We find in agreement with experimental observations that TEET proceeds through branch B. The TEET process toward branch B pigment is found to be significantly faster than the hypothetical process proceeding through branch A pigments with ps and ms time scales, respectively. Our calculations find that conformational differences play a major role in this branch asymmetry in TEET, where the dielectric environment asymmetry plays only a secondary role in directing the TEET to proceed through branch B. We also address TEET processes asserting the role of carotenoid as the final triplet energy acceptor and in a mutant form, where the branch pigments adjacent to P are replaced by bacteriopheophytins. The necessary electronic excitation energies and electronic state couplings are calculated by the recently developed polarization-consistent framework combining a screened range-separated hybrid functional and a polarizable continuum mode. The polarization-consistent potential energy surfaces are used to parametrize the quantum mechanical approach, implementing Fermi's golden rule expression of the TEET rate calculations.

Solvent Dependent Nuclear Magnetic Resonance Molecular Parameters Based on a Polarization Consistent Screened Range Separated Hybrid Density Functional Theory Framework.

Nuclear magnetic resonance (NMR) properties of solvated molecules are significantly affected by the solvent. We, therefore, employ a polarization consistent framework that efficiently addresses the solvent polarizing environment effects. Toward this goal a dielectric screened range separated hybrid (SRSH) functional is invoked with a polarizable continuum model (PCM) to properly represent the orbital gap in the condensed phase. We build on the success of range separated hybrid (RSH) functionals to address the erroneous tendency of traditional density functional theory (DFT) to collapse the orbital gap. Recently, the impact of RSH that properly opens up the orbital gap in gas-phase calculations on NMR properties has been assessed. Here, we report the use of SRSH-PCM that produces properly solute orbital gaps in calculating isotropic nuclear magnetic shielding and chemical shift parameters of molecular systems in the condensed phase. We show that in contrast to simpler DFT-PCM approaches, SRSH-PCM successfully follows expected dielectric constant trends.

Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 package.

This article summarizes technical advances contained in the fifth major release of the Q-Chem quantum chemistry program package, covering developments since 2015. A comprehensive library of exchange-correlation functionals, along with a suite of correlated many-body methods, continues to be a hallmark of the Q-Chem software. The many-body methods include novel variants of both coupled-cluster and configuration-interaction approaches along with methods based on the algebraic diagrammatic construction and variational reduced density-matrix methods. Methods highlighted in Q-Chem 5 include a suite of tools for modeling core-level spectroscopy, methods for describing metastable resonances, methods for computing vibronic spectra, the nuclear-electronic orbital method, and several different energy decomposition analysis techniques. High-performance capabilities including multithreaded parallelism and support for calculations on graphics processing units are described. Q-Chem boasts a community of well over 100 active academic developers, and the continuing evolution of the software is supported by an "open teamware" model and an increasingly modular design.

Discovery and characterization of an acridine radical photoreductant.

Photoinduced electron transfer (PET) is a phenomenon whereby the absorption of light by a chemical species provides an energetic driving force for an electron-transfer reaction1-4. This mechanism is relevant in many areas of chemistry, including the study of natural and artificial photosynthesis, photovoltaics and photosensitive materials. In recent years, research in the area of photoredox catalysis has enabled the use of PET for the catalytic generation of both neutral and charged organic free-radical species. These technologies have enabled previously inaccessible chemical transformations and have been widely used in both academic and industrial settings. Such reactions are often catalysed by visible-light-absorbing organic molecules or transition-metal complexes of ruthenium, iridium, chromium or copper5,6. Although various closed-shell organic molecules have been shown to behave as competent electron-transfer catalysts in photoredox reactions, there are only limited reports of PET reactions involving neutral organic radicals as excited-state donors or acceptors. This is unsurprising because the lifetimes of doublet excited states of neutral organic radicals are typically several orders of magnitude shorter than the singlet lifetimes of known transition-metal photoredox catalysts7-11. Here we document the discovery, characterization and reactivity of a neutral acridine radical with a maximum excited-state oxidation potential of -3.36 volts versus a saturated calomel electrode, which is similarly reducing to elemental lithium, making this radical one of the most potent chemical reductants reported12. Spectroscopic, computational and chemical studies indicate that the formation of a twisted intramolecular charge-transfer species enables the population of higher-energy doublet excited states, leading to the observed potent photoreducing behaviour. We demonstrate that this catalytically generated PET catalyst facilitates several chemical reactions that typically require alkali metal reductants and can be used in other organic transformations that require dissolving metal reductants.

Screened Range-Separated Hybrid Functional with Polarizable Continuum Model Overcomes Challenges in Describing Triplet Excitations in the Condensed Phase Using TDDFT.

Long range-corrected (LRC) or range-separated hybrid (RSH) functionals where the long-range (LR) limit of electronic interactions is set to the exact exchange have been shown to correct the tendency of traditional density functional theory (DFT) to underestimate the frontier orbital gap. Consequently, the use of such functionals in calculating electronic excited states using linear response based time-dependent DFT (TDDFT) has been successful in correcting the tendency for underestimating the energies of charge transfer states by DFT-based calculations. More recently formulations of functionals that attenuate the LR limit to address condensed-phase effects to polarize the electronic density have been reported. In particular screened RSH (SRSH) combined with polarizable continuum model (PCM) was benchmarked successfully in reproducing the fundamental gap and charge transfer state energies of molecular systems in the condensed phase. Here we use SRSH-PCM to address triplet excited states, and show its success in obtaining correspondence of the low-lying triplet states to the singlet-triplet gap in a similar way that the fundamental orbital gap corresponds to electron removal and addition energies. Importantly, the accuracy of the SRSH-PCM in calculating triplet excitations stands on the polarization consistent framework in addressing the scalar dielectric constant and without affecting the optimal tuning by triplet energies. The prospect of even further improving the SRSH-PCM accuracy in calculating triplet states can be achieved by optimal tuning on the basis of the spin multiplicity gap.