Excited S1 Research Articles

Role of Dielectric Screening in Calculating Excited States of Solvated Azobenzene: A Benchmark Study Comparing Quantum Embedding and Polarizable Continuum Model for Representing the Solvent.

The low energy excited states of the conformational isomers of solvated azobenzene are calculated with several DFT methods accounting for the solute-solvent interaction implicitly with the polarizable continuum model or explicitly with subsystem DFT. For the latter, embedding potentials are calculated for 21 sampled snapshots of the solvent molecules. First, we find that accounting for the solvent implicitly or explicitly has little effect on the predicted cis-trans S1 excitation energy gap. Second, we find that azobenzene's S1 cis and trans energies are accurate as long as a screened range-separated hybrid exchange-correlation functional is employed. Finally, we also tested a simplified workflow whereby a single, averaged, embedding potential is used. Unfortunately, we find larger deviations against the experiment for the simplified workflow. This highlights a basic flaw in the approach, where the time scale of solvent averaging is much longer than that of the solute's electronic polarization.

Excited states of spin-(3/2) doubly-heavy baryons within the QCD sum rules method

Within the framework of the QCD sum rules method, the masses and pole residues of the excited states 2S and 1P of the doubly-heavy spin-(3/2) baryons Xi _{cc}^*, Xi _{bb}^*, Xi _{bc}^*, Omega _{cc}^*, Omega _{bb}^*, and Omega _{bc}^* are investigated. The excited state masses and pole residues are predicted with reasonable accuracy. We expect that soon, the current predictions can be tested against future experimental data.

Identification of excimer delayed fluorescence by Protoporphyrin IX: A novel access to local chromophore concentration?

Protoporphyrin IX (PpIX) is a molecule produced in the mitochondria following the administration of its approved precursor, aminolevulinic acid (ALA). Strong light absorber at different wavelengths in the visible range, PpIX is extensively used as a photosensitizer (PS) for Photodynamic Therapy (PDT). PpIX is also an ideal molecular probe for the quantification of the tissue oxygen partial pressure (pO2), as its delayed fluorescence (DF) is quenched by oxygen, creating a direct relationship between the DF lifetime and the pO2. A limitation of both techniques is the ignorance of the PpIX concentration in tissues when the pO2 is measured or during PDT. In this study, the prompt (PF) and delayed fluorescence of PpIX dissolved in DiMethylFormamide (DMF) were acquired, in absence of oxygen, at different PpIX concentrations. Measurements of the PpIX emission for different excitation energies and temperatures, as well as spectral considerations led to the conclusion that E-type (thermal) DF was the dominant DF mechanism at low PpIX excited states concentrations (density of absorbed energy Hε[PpIX]<1 μJ. cm-3, H:excitation radiant exposure per pulse, ε: molar extinction coefficient at excitation wavelength) while P-type (Triplet Triplet Annihilation) DF took place at higher excited states concentrations (Hε[PpIX]>10 μJ. cm-3). The gradual development of a strong, red-shifted structureless DF peak at 670nm, invisible in the PF and absorption spectra, strongly points towards the first observation of PpIX excimer DF (EDF). It appears that, similarly to other aromatic molecules, PpIX excimers can be formed either by the encounter of two molecules in the first excited triplet state T1, or by the reaction of an excited singlet S1 with a triplet T1. Excimer DF could be beneficially used to determine the local concentration of PpIX, as the initial DF intensity ratio I0670/I0630 is linearly correlated with the local PpIX concentration, and thus rises up to the challenge of PpIX based pO2 measurement and PDT. This work could also pave the way for a fine comprehension of the production, diffusion and catabolization of PpIX in biological tissues.

Second-Order Active-Space Embedding Theory.

Quantum embedding schemes are a promising way to extend multireference computations to large molecules with strong correlation effects localized on a small number of atoms. This work introduces a second-order active-space embedding theory [ASET(2)] which improves upon mean-field frozen embedding by treating fragment-environment interactions via an approximate canonical transformation. The canonical transformation employed in ASET(2) is formulated using the driven similarity renormalization group. The ASET(2) scheme is benchmarked on the N═N bond dissociation in pentyldiazene, the S0 to S1 excitation in 1-octene, and the interaction energy of the O2-benzene complex. The ASET(2) explicit treatment of fragment-environment interactions beyond the mean-field level generally improves the accuracy of embedded computations, and it becomes necessary to achieve an accurate description of excitation energies of 1-octene and the singlet-triplet gap of the O2-benzene complex.

Segmented correlation consistent basis sets for the 4d and 5d transition metals.

The cc-pVnZ-PP and cc-pwCVnZ-PP (n = D, T, Q, 5) pseudopotential-based correlation consistent basis sets for the 4d and 5d transition metals were reoptimized to have segmented contraction schemes. Computed ionization potentials and dns2 → dn+1s1 excitation energies computed at the coupled cluster level of theory with single, double, and perturbative triple excitations using the segmented basis sets approximate the result obtained with the generally contracted basis sets with mean absolute deviations (MADs) within 0.75kcal mol-1 for the ionization energies and 2kcal mol-1 for the excitation energies with respect to the results obtained with the generally contracted basis. The segmented basis sets also retain the systematically convergent behavior of the correlation consistent basis sets with MADs within 0.61kcal mol-1 with respect to the generally contracted basis for properties extrapolated to the complete basis set limit. The segmented nature of the seg-cc-pVnZ-PP and seg-cc-pwCVnZ-PP basis sets enables significant performance improvements when using algorithms with an a priori treatment of the contraction coefficients with average speedups in the time required to form the Fock matrix ranging from 6.1× for the seg-cc-pVDZ-PP basis sets to 53.8× for the seg-cc-pV5Z-PP basis sets.

Lactic acid photochemistry following excitation of S0 to S1 at 220 to 250 nm

AbstractLactic acid, a small α‐hydroxy acid, is a multifunctional molecule that is prevalent on modern Earth and found in abiotic environments. Recently, there has been interest in the photochemistry of carboxylic acids in general. Specifically, the photochemistry of lactic acid, due to its prevalence and functionality, has garnered attention by the biomass valorization and abiotic chemistry communities. However, aqueous lactic acid photochemistry studies are limited, and gas‐phase lactic acid photolysis had not been performed. This work combines theory and experiments to explore the gas‐phase and aqueous phase photochemistry of lactic acid following excitation of S0 to S1 at 220–250 nm. We find that lactic acid primarily photodecomposes via decarboxylation in both phases. In the gas phase, secondary chemistry leads to mainly CO2 and CO, while in the aqueous phase, subsequent radical chemistry leads to a variety of products with one to four carbons. Isotopic substitutions, including the use of 13C tagged lactic acid and using D2O as a solvent, are used to infer mechanistic pathways for the major photolysis products. Computation shows that individual conformers may contribute to the overall photochemistry to a different degree than their relative abundance would suggest. The identified products and proposed mechanisms shown here serve to illustrate the photochemistry of lactic acid in the presence of high‐energy ultraviolet radiation. This knowledge may aid process and catalyst design for biomass valorization/organic synthesis and may provide insight into abiotic chemistry in environments exposed to high energy ultraviolet radiation.

Simulations of x-ray absorption spectra for CO desorbing from Ru(0001) with transition-potential and time-dependent density functional theory approaches.

The desorption of a carbon monoxide molecule from a Ru(0001) surface was studied by means of X-ray Absorption Spectra (XAS) computed with Transition Potential (TP-DFT) and Time Dependent (TD-DFT) DFT methods. By unraveling the evolution of the CO electronic structure upon desorption, we observed that at 2.3 Å from the surface, the CO molecule has already predominantly gas-phase character. While C 1s XAS is quite insensitive to changes in the C–O bond length, the O 1s excitation is very sensitive with the π* coming down in energy upon CO bond stretching, which competes with the increase in orbital energy due to the repulsive interaction with the metallic surface. We show in a systematic way that the TP-DFT method can describe the XAS rather well at the endpoints (chemisorbed and gas phase) but is affected by artificial charge transfer and/or incorrect spin treatment in the transition region in cases like CO, where there are low-lying π* orbitals and large exchange interactions between the core 1s and valence-acceptor π* orbitals. As an alternative, we demonstrate by comparing with experimental data that a linear response approach using TD-DFT employing common exchange-correlation functionals and finite-size clusters can yield a good description of the spectral evolution of the 1s → π* transition with correct spin and gas-to-chemisorbed chemical shifts in good agreement with experiment.

Providing theoretical insight into the role of symmetry in the photoisomerization mechanism of a non-symmetric dithienylethene photoswitch.

Dithienylethene (DTE) molecular photoswitches have shown to be excellent candidates in the design of efficient optoelectronic devices, due to their high photoisomerization quantum yield (QY), for which symmetry is suggested to play a crucial role. Here, we present a theoretical study on the photochemistry of a non-symmetric dithienylethene photoswitch, with a special emphasis on the effect of asymmetric substitution on the photocyclization and photoreversion mechanisms. We used the Spin-Flip Time Dependent Density Functional Theory (SF-TDDFT) method to locate and characterize the main structures (conical intersections and minima) of the ground state and the first two excited states, S1 and S2, along the ring-opening/closure reaction coordinate of the photocyclization and photoreversion processes, and to identify the important coordinates governing the radiationless decay pathways. Our results suggest that while the main features that characterize the photoisomerization of symmetric DTEs are also present for the photoisomerization of the non-symmetric DTE, the lower energy barrier on S1 along the cycloreversion reaction speaks in favor of a more efficient and therefore a higher cycloreversion QY for the non-symmetric DTEs, making them a better candidate for molecular optoelectronic devices than their symmetric counterparts.

Ultrafast exciton delocalization and localization dynamics of a perylene bisimide quadruple π-stack: a nonadiabatic dynamics simulation.

Unraveling the photogenerated exciton dynamics of π-stacked molecular aggregates is of great importance for both fundamental studies and industrial applications. Among various π-stacked molecular aggregates, perylene tetracarboxylic acid bisimide (PBI) based aggregates are regarded as one of the prototypes due to their inherent high fluorescence quantum yield and excellent photostability and flexibility in controlling intermolecular forces via chemical modifications. However, the exciton dynamics of these PBI based aggregates remain elusive up to now. In this work, we have first employed LR-TDDFT-based nonadiabatic dynamics simulations and static electronic structure calculations to investigate the ultrafast exciton dynamics of a newly synthesized perylene bisimide quadruple (PBQ) π-stack. Upon photoexcitation, the S6 to S10 states are the most likely populated excited states, which can be regarded as a combination of local excited (LE) excitons and charge transfer (CT) excitons of those four PBI chromophores. Then, the excited PBQ π-stack relaxes ultrafast to the lowest lying excited S1 state within 500 fs, which is accompanied by the complicated exciton conversion as well as exciton localization/delocalization dynamics. In short, the initially populated hybrid LE and CT excitons convert to the LE excitons of B/C and A/D, in which the LE excitons of B/C contribute the most (∼0.44) while the LE excitons of A/D also have minor contributions (0.21), indicating the formation of the localized excimer state. We use the notations A/B/C/D here to represent the four PBI fragments of PBQ π-stacks along the direction perpendicular to the PBI molecular plane. Additionally, using a recently defined root mean square deviation (RMSD) of electron and hole spatial distributions along three Cartesian coordinates, we could investigate the exciton localization/delocalization dynamics in a quantitative way. Our simulation results indicate that the photoinduced electrons and holes of the PBQ π-stack exhibit an ultrafast localization(∼10 fs)-delocalization(∼60 fs)-localization(∼200 fs) dynamics, during which both LE and CT excitons play crucial roles. Our present work is not only consistent with previous experimental studies, but also provides more detailed insights into the relevant processes, which might be useful for the future design of PBI based optoelectronic devices with improved performances.

Data-driven modeling of S0 → S1 excitation energy in the BODIPY chemical space: High-throughput computation, quantum machine learning, and inverse design.

Derivatives of BODIPY are popular fluorophores due to their synthetic feasibility, structural rigidity, high quantum yield, and tunable spectroscopic properties. While the characteristic absorption maximum of BODIPY is at 2.5eV, combinations of functional groups and substitution sites can shift the peak position by ±1eV. Time-dependent long-range corrected hybrid density functional methods can model the lowest excitation energies offering a semi-quantitative precision of ±0.3eV. Alas, the chemical space of BODIPYs stemming from combinatorial introduction of-even a few dozen-substituents is too large for brute-force high-throughput modeling. To navigate this vast space, we select 77 412 molecules and train a kernel-based quantum machine learning model providing <2% hold-out error. Further reuse of the results presented here to navigate the entire BODIPY universe comprising over 253 giga (253 × 109) molecules is demonstrated by inverse-designing candidates with desired target excitation energies.

Hydrocarboxyl Radical as a Product of α-Alanine Ultraviolet Photolysis.

UV photodissociation of α-alanine was studied by parahydrogen matrix isolation infrared spectroscopy. The temporal behavior of Fourier transform infrared spectra revealed that UV irradiation at 213 nm yielded the HOCO radical as a direct photoproduct from the S2 excited state. The concentration of HOCO quickly approached a steady state due to secondary photodissociation of HOCO to produce CO2 + H or CO + OH. On the other hand, no photoproducts were detected by S1 excitation at 266 nm. Irradiation of fully deuterated α-alanine at 213 nm yielded ∼2 times more cis-DOCO radicals than the lower energy isomer trans-DOCO, indicating that the conformation of the hydroxyl group is fairly well-preserved upon photodissociation of α-alanine. The present study suggests that HOCO may be a good tracer species in the search for amino acids in interstellar space.

Plasma Confined Ground and Excited State Helium Atom: A Comparison Theorem Study Using Variational Monte Carlo and Lagrange Mesh Method

The energy eigenvalues of the ground state helium atom and lowest two excited states corresponding to the configurations 1s2s embedded in the plasma environment using Hulthén, Debye–Hückel and exponential cosine screened Coulomb model potentials are investigated within the variational Monte Carlo method, starting with the ultracompact trial wave functions in the form of generalized Hylleraas–Kinoshita functions and Guevara–Harris–Turbiner functions. The Lagrange mesh method calculations of energy are reported for the He atom in the ground and excited 1S and 3S states, which are in excellent agreement with the variational Monte Carlo results. Interesting relative ordering of eigenvalues are reported corresponding to the different screened Coulomb potentials in the He ground and excited electronic states, which are rationalized in terms of the comparison theorem of quantum mechanics.

Simulation of Low-Lying Singlet and Triplet Excited States of Multiple-Resonance-Type Thermally Activated Delayed Fluorescence Emitters by Delta Self-Consistent Field (ΔSCF) Method.

The delta self-consistent field (ΔSCF) method was applied to the simulation of low-lying singlet and triplet excited states of multiple-resonance (MR)-type thermally activated delayed fluorescence (TADF) molecules, which form a promising group for organic light-emitting diode (OLED) emitters. A comparison with the experimental values of 13 emitters from the literature showed that ΔSCF gave fairly accurate S1 and T1 excitation energies (mean absolute errors (MAEs) of 0.092 and 0.055 eV, respectively) as well as quite accurate ΔEST (S1-T1 gap, MAE of 0.041 eV), which could not be calculated with sufficient accuracy by the conventional time-dependent density functional theory (TDDFT). ΔSCF also demonstrated its utility for the analysis of photophysical properties through a simulation of the reverse intersystem crossing (RISC) process of an MR-type emitter.

Isomer-selective dative bond O→M (M = Si, Ge) for designing new photochromic hemi-indigo systems

New photochromic systems MY2X-HI (M = Si, Ge) were designed (at the DFT level of theory) by replacing the hydrogen atom in the nitrogen of the pyrrole ring of hemi-indigo, HI, with silyl- or germyl-substituents. The E isomers of MY2X-HI contain a dative bond O→M (pentacoordinated atom M) both in the ground S0 and in the excited S1 states. This leads to a significant difference in the absorption and fluorescence maxima (λfl - λabs) of the Z and E forms of hypervalent hemi-indigos; this difference is more than twice that of the parent HI. There is a trend to increasing separation of first π→π* absorption bands of the E and Z isomers of MY2X-HI with the increase in their relative stability.

Tetraaryldiborane(4) Can Emit Dual Fluorescence Responding to the Structural Change around the B-B Bond.

We report the successful synthesis of tetramesityldiborane(4) (Mes4 B2 ) through the reductive coupling of a dimesitylborinium ion. Owing to the steric protection conferred by the mesityl groups, Mes4 B2 shows exceptional chemical stability and remains intact in water. Single-crystal X-ray analysis revealed that Mes4 B2 has an orthogonal geometry, where the B-B center is completely hidden by the mesityl groups. Remarkably, Mes4 B2 emits dual fluorescence at 460 and 620 nm, both in solution and in the solid state. Theoretical calculations showed that Mes4 B2 in the excited S1 state adopts a twisted or planar geometry, which is responsible for the shorter- or longer-wavelength fluorescence, respectively. The intensity ratio of the dual fluorescence is sensitive to the viscosity of the medium, which suggests that Mes4 B2 has potential as a ratiometric viscosity sensor.

Tetraaryldiborane(4) Can Emit Dual Fluorescence Responding to the Structural Change around the B–B Bond

AbstractWe report the successful synthesis of tetramesityldiborane(4) (Mes4B2) through the reductive coupling of a dimesitylborinium ion. Owing to the steric protection conferred by the mesityl groups, Mes4B2 shows exceptional chemical stability and remains intact in water. Single‐crystal X‐ray analysis revealed that Mes4B2 has an orthogonal geometry, where the B–B center is completely hidden by the mesityl groups. Remarkably, Mes4B2 emits dual fluorescence at 460 and 620 nm, both in solution and in the solid state. Theoretical calculations showed that Mes4B2 in the excited S1 state adopts a twisted or planar geometry, which is responsible for the shorter‐ or longer‐wavelength fluorescence, respectively. The intensity ratio of the dual fluorescence is sensitive to the viscosity of the medium, which suggests that Mes4B2 has potential as a ratiometric viscosity sensor.

Positional and Conformational Isomerism in Hydroxybenzoic Acid: A Core-Level Study and Comparison with Phenol and Benzoic Acid.

Three positional isomers of hydroxybenzoic acid, as well as phenol and benzoic acid, were studied using core-level photoemission and X-ray absorption spectroscopies, supported by quantum chemical calculations. While 2-hydroxybenzoic (salicylic) acid exists as a single conformer with an internal hydrogen bond, 3- and 4-hydroxybenzoic acids are mixtures of multiple conformers. The effects due to isomerism are clearly seen in the C 1s and O 1s photoelectron spectra, whereas the conformational effects on the binding energies are less pronounced. The O 1s photoelectron spectrum of salicylic acid is significantly different from that of the other two isomers, providing a signature of the hydrogen bond. In contrast, the oxygen K edge X-ray absorption spectra of the three hydroxybenzoic acids show only minor differences. The salicylic acid absorption spectrum at the carbon K edge shows a more resolved vibrational structure than the spectra of the other molecules, which can be explained in part by the existence of a single conformer. Our theoretical study of vibrational excitations in the lowest C 1s absorption bands of salicylic and 4-hydroxybenzoic acids indicates that the observed structure can be assigned to 0-0 lines of various electronic transitions since most of the totally symmetric vibrational modes with sufficiently large frequencies to be resolved are predicted to be inactive. Significant sensitivity of the C 1s excitations in 3-hydroxybenzoic acid to rotational conformerism was predicted but not observed due to spectral crowding.

UV Excitation of Carotenoid Binding Proteins OCP and HCP: Excited‐State Dynamics and Product Formation

AbstractOver the last decade the orange carotenoid protein (OCP) gained attention due to its role in photoprotection in cyanobacteria. Recently, other carotenoid binding proteins such as helical carotenoid proteins (HCPs) have been identified and characterized, although the function of the HCPs is not yet clarified. Here we have examined OCP1 and two HCPs, HCP2 and HCP3, from Tolypothrix PCC 7601 by ultrafast spectroscopy after excitation of both carotenoid canthaxanthin and amino acids tryptophan and tyrosine in UV at 275 nm. We find that the canthaxanthin S1 lifetime remains the same 3.5 ps as for excitation of the carotenoid S2 state, but the S* signal is significantly amplified by UV excitation. In contrast to the S2 excitation, we observe a formation of the canthaxanthin radical cation at 900 nm for all three proteins after 275 nm excitation. In OCP1, UV light also enhances the amplitude of spectral band centered at 550 nm at longer delays. This band likely corresponds to the first photoproduct of the OCP photocycle, suggesting that excess energy excitation and/or direct excitation of amino acids can enhance the product formation.

Nature of the Ligand-Centered Triplet State in Gd3+ β-Diketonate Complexes as Revealed by Time-Resolved EPR Spectroscopy and DFT Calculations.

A series of Gd3+ complexes (Gd1–Gd3) with the general formula GdL3(EtOH)2, where L is a β-diketone ligand with polycyclic aromatic hydrocarbon substituents of increasing size (1–3), was studied by combining time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and DFT calculations to rationalize the anomalous spectroscopic behavior of the bulkiest complex (Gd3) through the series. Its faint phosphorescence band is observed only at 80 K and it is strongly red-shifted (∼200 nm) from the intense fluorescence band. Moreover, the TR-EPR spectral analysis found that triplet levels of 3/Gd3 are effectively populated and have smaller |D| values than those of the other compounds. The combined use of zero-field splitting and spin density delocalization calculations, together with spin population analysis, allows us to explain both the large red shift and the low intensity of the phosphorescence band observed for Gd3. The large red shift is determined by the higher delocalization degree of the wavefunction, which implies a larger energy gap between the excited S1 and T1 states. The low intensity of the phosphorescence is due to the presence of C–H groups which favor non-radiative decay. These groups are present in all complexes; nevertheless, they have a relevant spin density only in Gd3. The spin population analysis on NaL models, in which Na+ is coordinated to a deprotonated ligand, mimicking the coordinative environment of the complex, confirms the outcomes on the free ligands.

Collisional excitation in Neon-like projectiles scattered from Al

We performed experiments of electron emission in the interaction of singly charged Na+ and Ne+ with Al surfaces. We compare Auger emission from sodium and neon projectiles excited in the 2p level by promotion of the 4fσ molecular orbital of the transient molecule, formed during a binary collision with an Al target atom. Doubly excited states are formed in single scattering events involving neutral Neon projectiles and neon-like Na+ ions. Measurements performed with Neon projectiles at impact energy up to 10 keV reveal the onset 2s excitation via promotion of the 3pσ molecular orbital. The fact, that several promotion processes become active with increasing ion energy, has implication on recent energy loss and energy deposition studies.