Excited S1 Research Articles

Luminescence of isoelectronic lanthanide pairs (Ln2+/Ln3+): A relative compression factor for isoelectronic Ln 4fn levels

Luminescent trivalent lanthanides (Ln3+) are utilised extensively in photonic and optoelectronic devices. Luminescent divalent lanthanides (Ln2+) are less frequently applied, despite their desirable 5d electronic properties and similar 4f electronic properties. We report on the luminescence of several isoelectronic lanthanide pairs (Ln3+/Ln2+) that possess the same 4fn configurations but different nuclear charges. The intraconfigurational and interconfigurational transitions of divalent Nd, Sm, Eu, Dy, Ho, Tm and Yb in NaMgF3 are compared to those transitions of trivalent counterparts in NaMgF3 and similar hosts. The 4fn(2S+1LJ) levels of Ln2+ ions are compressed by a factor ξ, relative to the isoelectronic Ln3+. The factor varies within each 4fn configuration with the energy of excited 2S’+1LJ’ states. We define an alternative factor ξ′ that corrects for the intra-ion dependence by introducing a power law dependence on the excited state energies. The inter-ion dependence correlates with the spin-orbit coupling parameters of the isoelectronic ions.

Soft X-Ray-induced Dimerization of Methane

Carbon 1s excitation of methane, CH4, has been studied in the gas phase using the ion trap integrated with the photon–ion instrument at PETRA III/DESY and soft X-rays from the beamline P04. The created photoions are stored within the ion trap so that in further steps the photoions can undergo reactions with neutral methane molecules. The ionic photoproducts as well as reaction products created thereby are mass-over-charge analyzed by an ion time-of-flight spectrometer. Besides the photoions, product ions with up to three carbon atoms are found. In contrast to experiments using vacuum ultraviolet radiation, especially highly reactive product ions with a small number of hydrogen atoms such as and are found, which are important precursors for larger hydrocarbons such as C6H6. Possible production routes of the product ions are analyzed on the basis of a model that considers the probabilities for photofragmentation and the first subsequent chemical reaction step. The model indicates that the high degree of fragmentation by photons with energies around 280 eV is favoring these products. The results of the measurements show that the products like and can be generated by a single collision of the ionization product with neutral methane. The results suggest that soft X-rays might be important for chemical reactions in planetary atmospheres, which has usually not been taken into account. However, due to the high degree of fragmentation and large cross sections involved, they can have a large influence even when the corresponding photon flux is rather small.

Tailoring Carbene-Metal-Amides for Thermally Activated Delayed Fluorescence: A Computationally Guided Study on the Effect of Cyclic (Alkyl)(amino)carbenes.

Gold-centered carbene-metal-amides (CMAs) containing cyclic (alkyl)(amino)carbenes (CAACs) are promising emitters for thermally activated delayed fluorescence (TADF). Aiming at the design and optimization of new TADF emitters, we report a density functional theory study of over 60 CMAs with various CAAC ligands, systematically evaluating computed parameters in relation to photoluminescence properties. The CMA structures were primarily selected based on experimental synthesis prospects. We demonstrate that TADF efficiency of the CMA materials originates from a compromise between oscillator strength coefficients and exchange energy (ΔEST). The latter is governed by the overlap of HOMO and LUMO orbitals, where HOMO is localized on the amide and LUMO over the Au-carbene bond. The S0 ground and excited T1 states of the CMAs adopt approximately coplanar geometry of carbene and amide ligands, but rotate perpendicular in the excited S1 states, resulting in degeneracy or near-degeneracy of S1 and T1, accompanied by a decrease in the S1-S0 oscillator strength from its maximum at coplanar geometries to near zero at rotated geometries. Based on the computations, promising new TADF emitters are proposed and synthesized. Bright CMA complex (Et2CAAC)Au(carbazolide) is obtained and fully characterized in order to demonstrate that excellent stability and high radiative rates up to 106 s-1 can be obtained for the gold-CMA complexes with small CAAC-carbene ligands.

Unveiling controlling factors of the S0/S1 minimum-energy conical intersection (3): Frozen orbital analysis based on the spin-flip theory.

Conical intersections (CIs), which indicate the crossing of two or more adiabatic electronic states, are crucial in the mechanisms of photophysical, photochemical, and photobiological processes. Although various geometries and energy levels have been reported using quantum chemical calculations, the systematic interpretation of the minimum energy CI (MECI) geometries is unclear. A previous study [Nakai et al., J. Phys. Chem. A 122, 8905 (2018)] performed frozen orbital analysis (FZOA) based on time-dependent density functional theory (TDDFT) at the MECI formed between the ground and first electronic excited states (S0/S1 MECI), thereby inductively clarifying two controlling factors. However, one of the factors that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy gap became close to the HOMO-LUMO Coulomb integral was not valid in the case of spin-flip TDDFT (SF-TDDFT), which is frequently used as a means of the geometry optimization of MECI [Inamori et al., J. Chem. Phys. 152, 144108 (2020)]. This study revisited the controlling factors using FZOA for the SF-TDDFT method. Based on spin-adopted configurations within a minimum active space, the S0-S1 excitation energy is approximately represented by the HOMO and LUMO energy gap ΔεHL, a contribution from Coulomb integrals JHL″ and that from the HOMO-LUMO exchange integral KHL″. Furthermore, numerical applications of the revised formula at the SF-TDDFT method confirmed the control factors of S0/S1 MECI.

Synthetic Model for FRET Constructed from Covalently Linked Porphyrin Dimers through a Pyrene Bridge.

We report the synthesis and characterization of two porphyrin arrays C6F5-PyZnDP and Mes-PyZnDP covalently linked by a pyrene moiety which differs from their substituents at their meso-positions. The key precursor bis-dipyrromethane linked with a pyrene bridge was prepared by the acid-catalyzed condensation of pyrene-1,6-dialdehyde with excess pyrrole. The synthesis of C6F5-PyZnDP was carried out via two different synthetic routes, with one being efficient over the other. Therefore, the superior route was employed for the synthesis of C6F5-PyZnDP and Mes-PyZnDP. Both the free base and metalated diporphyrins show bathochromically shifted absorption and intense red emission due to the extended π-conjugation through pyrene and porphyrins. The single-crystal X-ray structure reveals an orthogonal orientation of pyrene in between the two planar porphyrins and a slipped stacked packing arrangement in the crystal structure with large meso-meso distances. DFT analysis of both the ground state and the excited S1 state of the macrocycles indicates the difference in the HOMO and LUMO contribution in both the states arising from slight twisting from the mean orthogonal position in the excited state. Further, the Förster energy transfer (FRET) efficiencies from pyrene (donor) to the covalently linked Zn-porphyrins (acceptor) are estimated to be 85 and 91% for Mes-PyZnDP and C6F5-PyZnDP, respectively.

L-Shell Photoionization of Magnesium-like Ions with New Results for Cl5+

This study reports on the absolute photoionization cross sections for the magnesium-like Cl5+ ion over the 190–370 eV photon energy range, corresponding to the L-shell (2s and 2p subshells) excitation regime. The experiments were performed using the Multi-Analysis Ion Apparatus (MAIA) on the PLéIADES beamline at the SOLEIL synchrotron radiation storage ring facility. Single and double ionization ion yields, produced by photoionization of the 2p subshell of the Cl5+ ion from the 2p63s2 1S0 ground state and the 2p63s3p 3P0,1,2 metastable levels, were observed, as well as 2s excitations. Theoretical calculations of the photoionization cross sections using the Multi-Configuration Dirac-Fock and R-matrix approaches were carried out, and the results were compared with the experimental data. The Cl5+ results were examined within the overall evolution of L-shell excitation for the early members of the Mg-like isoelectronic sequence (Mg, Al+, Si2+, S4+, Cl5+). Characteristic photon energies for P3+ were estimated by interpolation.

The impact of π-π stacking interactions on photo-physical properties of hydroxyanthraquinones

The impact of π-π stacking interactions on photo-physical properties of hydroxyanthraquinone (HA) has been investigated using the density functional (DFT) and time-dependent density functional theory (TD-DFT) calculations in the gas phase and solution media. The vertical transition is characterized with strong HOMO-LUMO transition in the complexes. The intramolecular hydrogen bond (IHB) made in the HA and π-π complexes is strengthened after S0 → S1 excitation, such that the proton transfers is facilitated in the first excited state. The complexes exhibit an exothermic excited state intramolecular proton transfer (ESIPT) in the solution media, which is a barrierless process for some complexes. The π-π stacking interaction affects the absorption and emission bands of HA, and provides a large Stokes shift. This indicates the desirable fluorescence properties of π-π complexes, which are cross-validated by geometries, potential energy curve scannings, electronic and vibrational spectra, and frontier molecular orbital analyses.

Photodissociation dynamics of tetrahydrofuran at 193 nm.

Tetrahydrofuran (THF), a cyclic ether with the chemical formula C4H8O, can be considered the simplest analog of the deoxyribose backbone component of deoxyribonucleic acid (DNA). As such, it provides a useful model for probing the photochemistry of such biomolecular motifs. We present a velocity-map imaging study into the ultraviolet dissociation of THF at a wavelength of 193 nm. Excitation to the S1 state occurs via a 3s ← n transition involving a lone-pair electron on the oxygen atom, and has been shown by other authors to result in rapid ring opening via cleavage of one of the C-O bonds to form a ring-opened C4H8O diradical, followed by C-C bond cleavage over a longer timescale to form either OCH2 + C3H6 products (Channel 1a), HOCH2 + C2H5 products (Channel 1b), or OCH2CH2 + C2H4 products (Channel 2). The C2H4O products formed via Channel 2 are unstable on the timescale of our experiment and dissociate further to form CH3 and CHO. We also observe a number of minor products resulting from H or H2 loss from the primary photofragments. The speed distributions observed for all photofragments are broad, indicating excitation of a range of rotational and vibrational states of the products. The angular distributions of the photofragments show an interesting speed dependence: the slowest products have almost isotropic angular distributions, but the magnitude of the recoil anisotropy increases monotonically with photofragment speed. The fastest products exhibit highly anisotropic angular distributions, with the recoil anisotropy parameter β approaching its limiting value of -1 (-0.75 for Channel 1 and -0.5 for Channel 2). This behaviour is attributed to the range of timescales over which the diradical intermediate dissociates into the observed photofragments. Rapid dissociation leads to fast photofragments which retain the correlation between the transition dipole moment for the S1 ← S0 excitation (which lies perpendicular to the ring) and the photofragment velocities (which lie predominantly in the plane of the ring). Slow dissociation results in a high degree of energy redistribution into internal modes, slower photofragments, and loss of correlation between the photofragment velocities and the transition dipole. The higher barrier associated with dissociation via Channel 2 suggests somewhat longer lifetimes for the diradical intermediate and is consistent with a corresponding reduction in the maximum observed value for β.

Relaxation dynamics of high-energy excited states of carotenoids studied by UV excitation and pump-repump-probe transient absorption spectroscopy.

The excited states of carotenoids have been a subject of numerous studies. While a majority of these reports target the excited state dynamics initiated by the excitation of the S2 state, the upper excited state(s) absorbing in the UV spectral region (denoted as SUV) has been only scarcely studied. Moreover, the relation between the SUV and Sn, the final state of the well-known S1-Sn transition of carotenoids, remains unknown. To address this yet-unresolved issue, we compared the excited state dynamics of two carotenoids, namely, β-carotene and astaxanthin, after excitation of either the SUV or Sn state. The SUV state was excited directly by UV light, and the excitation of the Sn state was achieved via re-pumping the S1-Sn transition. The results indicated that direct SUV excitation produces an S1-Sn band that is significantly broader than that obtained after S2 excitation, most probably due to the generation of multiple S1 conformations produced by excess energy. No such broadening is observed if the Sn state is excited by the re-pump pulse. This shows that the Sn and SUV states are different, each initializing a specific relaxation pathway. We propose that the Sn state retains the coupled triplet pair character of the S1 state, while the SUV state is the higher state of Bu+ symmetry accessible by one-photon transition.

Jahn-Teller effects in initial and final states: high-resolution X-ray absorption, photoelectron and Auger spectroscopy of allene.

Carbon K-edge resonant Auger spectra of gas-phase allene following excitation of the pre-edge 1s → π* transitions are presented and analysed with the support of EOM-CCSD/cc-pVTZ calculations. X-Ray absorption (XAS), X-ray photoelectron (XPS), valence band and non-resonant Auger spectra are also reanalysed with a series of computational approaches. The results presented demonstrate the importance of including nuclear ensemble effects for simulating X-ray observables and as an effective strategy for capturing Jahn-Teller effects in spectra.

Low-lying doubly heavy baryons: Regge relation and mass scaling

In framework of heavy-diquark–light-quark endowed with heavy-pair binding, we explore excited baryons QQ^{prime }q containing two heavy quarks (QQ^{prime }=cc,bb,bc) by combining the method of Regge trajectory with the perturbative correction due to the heavy-pair interaction in baryons. Two Regge relations, one linear and the other nonlinear, are constructed semi-classically in the QCD string picture, and a mass scaling relation based on the heavy diquark–heavy antiquark symmetry are employed between the doubly heavy baryons and heavy mesons. We employ the ground-state mass estimates compatible with the observed doubly charmed baryon Xi _{cc} and spectra of the heavy quarkonia to determine the trajectory parameters and the binding energies of the heavy pair, and thereby compute the low-lying masses of the excited baryons Xi _{QQ^{prime }} and Omega _{QQ^{prime }} up to 2S and 1P excitations of the light quark and heavy diquark. The level spacings of heavy diquark excitations are found to be smaller generally than that of the light-quark excitations, in according with the nature of adiabatic expansion between the heavy and light-quark dynamics.

An exploration of excited-state properties of three hydroxyanthraquinone compounds from the marine crinoid Pterometra venusta

Three natural hydroxyanthraquinone compounds HAQ (1–3) extracted from the Marine Crinoid Pterometra venusta. In order to identify their photochemical and electronic excited state properties of them, the theoretical research of optoelectronic properties have been studied. Using density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, UV- absorbance and fluorescence emission spectra of HAQ (1–3) had been calculated. The results show that calculated spectra are very consistent with the experimental data. For S0 → S1 excitation, HAQ1 and HAQ2 are the local excitation of π-π*, while HAQ3 presents S0 → S1 as n-π*charge transfer excitation characteristic.

Charmonium spectrum in an unquenched quark model

The effects of virtual light quark pairs on the charmonium spectrum are studied. Pair creation is modelled with a ``$^{3}P_{0}$" vertex and intermediate states are summed up to 2S excitations. Quark model parameters are obtained by fitting to 12 well-known charmonium states, allowing for feedback between the decaying particle and the induced mass shifts. Both of these technical steps are new and improve agreement with the experimental spectrum. In general, the masses receive small shifts once model parameters are refit. This is true in almost cases except the $\chi_{cJ}(2P)$ multiplet, which experiences upwards mass shifts of order 150 MeV, has the ordering of the multiplet rearranged, and pushes the erstwhile $c\bar{c}$ ${2}^3P_1$ state well above $D^*\bar{D}$ threshold--observations that clarify the nature of the enigmatic $X(3872)$

Bottom‐Up Preparation of Twisted Graphene Nanoribbons by Cu‐Catalyzed Deoxygenative Coupling

AbstractGraphene nanoribbons (GNRs) are promising in organic optoelectronic materials, and their properties largely depend on the size, edge, and conformation. Herein, the fully armchair‐edged GNRs (AGNRs) with lengths up to 2.65 nm by using a Cu‐catalyzed deoxygenative coupling as a key step. The resulting AGNRs (2HBT, 3HBT, and 4HBT) possess highly twisted π‐scaffolds, and the torsion angles between the adjacent triphenylene moieties are larger than 32°, as proved by crystallographic analyses. Theoretical and spectroscopic studies show that the butoxy groups endow AGNRs with electron‐rich features, the extension of the π‐system from 2HBT to 4HBT reinforces S0→S1 excitation, and the distortion of the π‐scaffold enhances the fluorescence quantum yield (ΦF). In particular, 4HBT has the lowest oxidation potential (Eox1=0.55 V vs. SCE) and displays red fluorescence with a ΦF value of 81 %.

A variational model for the hyperfine resolved spectrum of VO in its ground electronic state.

A variational model for the infra-red spectrum of vanadium monoxide (VO) is presented, which aims to accurately predict the hyperfine structure within the VO XΣ-4 electronic ground state. To give the correct electron spin splitting of the XΣ-4 state, electron spin dipolar interaction within the ground state and the spin-orbit coupling between XΣ-4 and two excited states, AΠ4 and 1Σ+2, are calculated ab initio alongside hyperfine interaction terms. Four hyperfine coupling terms are explicitly considered: Fermi-contact interaction, electron spin-nuclear spin dipolar interaction, nuclear spin-rotation interaction, and nuclear electric quadrupole interaction. These terms are included as part of a full variational solution of the nuclear-motion Schrödinger equation performed using program Duo, which is used to generate both hyperfine-resolved energy levels and spectra. To improve the accuracy of the model, ab initio curves are subject to small shifts. The energy levels generated by this model show good agreement with the recently derived empirical term values. This and other comparisons validate both our model and the recently developed hyperfine modules in Duo.

Effect of Temperature on Photoisomerization Dynamics of a Newly Designed Two-Stroke Light-Driven Molecular Rotary Motor.

The working mechanism of conventional light-driven molecular rotary motors, especially Feringa-type motors, contains two photoisomerization steps and two thermal helix inversion steps. Due to the existence of a thermal helix inversion step, both the ability to work at lower temperatures and the rotation speed are limited. In this work, a two-stroke light-driven molecular rotary motor, 2-(1,5-dimethyl-4,5-dihydrocyclopenta[b]pyrrol-6(1H)-ylidene)-1,2-dihydro-3H-pyrrol-3-one (DDPY), is proposed, which is capable of performing unidirectional and repetitive rotation by only two photoisomerization (EP→ZP and ZP→EP) steps. With trajectory surface-hopping simulation at the semi-empirical OM2/MRCI level, the EP→ZP and ZP→EP nonadiabatic dynamics of DDPY were systematically studied at different temperatures. Both EP→ZP and ZP→EP photoisomerizations are on an ultrafast timescale (ca. 200–300 fs). The decay mode of EP→ZP photoisomerization is approximately bi-exponential, while that of ZP→EP photoisomerization is found to be periodic. For EP and ZP isomers of DDPY, after the S→S excitation, the dynamical processes of nonadiabatic decay are both followed by twisting about the central C=C double bond and the pyramidalization of the C atom at the stator-axle linkage. The effect of temperature on the nonadiabatic dynamics of EP→ZP and ZP→EP photoisomerizations of DDPY has been systematically investigated. The average lifetimes of the S excited state and quantum yields for both EP→ZP and ZP→EP photoisomerization are almost temperature-independent, while the corresponding unidirectionality of rotation is significantly increased (e.g., 74% for EP→ZP and 72% for ZP→EP at 300 K vs 100% for EP→ZP and 94% for ZP→EP at 50 K) with lowering the temperature.

Direct comparison of molecular-beam vs liquid-phase pump-probe and two-dimensional spectroscopy on the example of azulene.

Although azulene's anomalous fluorescence originating from S2 rather than from S1 is a textbook example for the violation of Kasha's rule, an understanding of the underlying processes is still a subject of investigation. Here, we use action-based coherent two-dimensional electronic spectroscopy (2DES) to measure a single Liouville-space response pathway from S0 via S1 to the S2 state of azulene. We directly compare this sequential excitation in the liquid phase detecting S2 fluorescence and in a molecular beam detecting photoionized cations, using the S2 anomalous emission to our advantage. We complement the 2DES study with pump-probe measurements of S1 excitation dynamics, including vibrational relaxation and passage through a conical intersection. A direct comparison of the liquid and gas phase allows us to assess the effect of the solvent and the interplay of intra- and intermolecular energy relaxation.

1,1,1,2-tetrafluoroethane photofragmentation: a translational kinetic energy release analysis in the EUV and X-ray energies range

A molecule with two or more atoms of the same element in distinct chemical environments is a trial system for probing site-specific fragmentation. In this context, special attention is deserved to 1,1,1,2-tetrafluoroethane (CF3CH2F), which has been the subject of numerous studies. This work discusses the effects of extreme ultraviolet (EUV) and soft X-ray irradiation on CF3CH2F from a dedicated translational kinetic energy release (KER) perspective. This analysis is achieved by evaluating the mean KER for its fragments at photon energies over 30–320 eV and computing the KER distribution (KERD) for the main fragments over the 282–320 eV range. The questions of interest from the point of view of the present study are twofold: (i) How do the mean KER of ionic fragments of the valence or core-excited CF3CH2F molecule change as a function of incident photon energy? (ii) Is there any evidence of site-specific or state-specific dissociation mechanisms in a molecule containing two carbon atoms in distinct chemical environments? From our results, lighter fragments showed to have their mean KER virtually following respective ion yields previously reported. And the overall learning is that the chemical environment associated with each C 1s excitation plays a role in differentiating the KER results.

A DFT Study towards the Amide cis‐trans Isomerization Process of the Myc‐Max Inhibitor Mycro 3 and Its Photophysical Properties; Synthesis and NMR Studies of the trans‐Conformation

Cis-trans isomerization and photophysical properties of the isomers have been examined via DFT calculations. The isomerization barrier is slightly affected by the solvent effect. Absorption and emission spectra of the isomers showed that mycro3 has the potential to be used as a photosensitizer additionally to its potential as an inhibitor of the MYC oncoprotein. Synthesis and NMR experiments are in good agreement with theoretical data.

Photon‐Correlation Studies on Multichromophore Macrocycles of Perylene Dyes

AbstractOrganic dyes offer unique properties for their application as room temperature single photon emitters. By means of photon‐correlation, the emission characteristics of macrocyclic para‐xylylene linked perylene bisimide (PBI) trimers and tetramers dispersed in polymethyl methacrylate matrices are analyzed. The optical data indicate that, despite of the strong emission enhancement of PBI trimers and tetramers according to their larger number of chromophores, the photon‐correlation statistics still obeys that of single photon emitters. Moreover, driving PBI trimers and tetramers at higher excitation powers, saturated emission behavior for monomers is found while macrocycle emission is still far‐off saturation but shows enhanced fluctuations. This observation is attributed to fast singlet–singlet annihilation, i.e., faster than the radiative lifetime of the excited S1 state, and the enlarged number of conformational arrangements of multichromophores in the polymeric host. Finally, embedding trimeric PBI macrocycles in active organic light‐emitting diode matrices, electrically driven bright fluorescence together with an indication for antibunching at room temperature can be detected. This, so far, has only been observed for phosphorescent emitters that feature much longer lifetimes of the excited states and, thus, smaller radiative recombination rates. The results are discussed in the context of possible effects on the g(2) behavior of molecular emitters.