Triplet Spin Multiplicities Research Articles

Excited-State Forces with the Gaussian and Augmented Plane Wave Method for the Tamm-Dancoff Approximation of Time-Dependent Density Functional Theory.

Augmented plane wave methods enable an efficient description of atom-centered or localized features of the electronic density, circumventing high energy cutoffs and thus prohibitive computational costs of pure plane wave formulations. To complement existing implementations for ground-state properties and excitation energies, we present the extension of the Gaussian and augmented plane wave method to excited-state nuclear gradients within the Tamm-Dancoff approximation of time-dependent density functional theory and its implementation in the CP2K program package. Benchmarks for a test set of 35 small molecules demonstrate that maximum errors in the nuclear forces for excited states of singlet and triplet spin multiplicity are smaller than 0.1 eV/Å. The method is furthermore applied to the calculation of the zero-phonon line of defective hexagonal boron nitride. This spectral feature is reproduced with an error of 0.6 eV in comparison to GW-Bethe-Salpeter reference computations and 0.4 eV in comparison to experimental measurements. Accuracy assessments and applications thus demonstrate the potential use of the outlined developments for large-scale applications on excited-state properties of extended systems.

Al2O Photochemistry

The chemistry within the interstellar medium (ISM) is notably influenced by the interplay between kinetics and photochemical processes, which play significant roles in both the formation and destruction of molecular species. This study focuses on theoretical investigations of Al2O photochemistry, aiming to elucidate the mechanisms underlying the production of AlO and Al in the VY-CMa star. Utilizing advanced theoretical methodologies, we explore the lowest electronic states with singlet and triplet spin multiplicities in linear Al2O. We investigated the photostability of Al2O in the near UV‒Vis region, revealing the low likelihood of photodissociation and photoconversion while suggesting the plausibility of fluorescence and phosphorescence phenomena. Calculations also identify three prominent peaks in the UV range at 261.5, 206.2, and 199 nm. Finally, Al2O is predicted to be photostable and cannot be the parent molecule of the diatomic AlO or even the astrochemical reservoir of atomic aluminum. These results contribute to improving the astronomical models in simulating aluminum chemistry in the ISM.

Observation of Long-Lived Charge-Separated States in Anthraquinone-Phenothiazine Electron Donor-Acceptor Dyads: Transient Optical and Electron Paramagnetic Resonance Spectroscopic Studies.

We prepared a series of phenothiazine (PTZ)-anthraquinone (AQ) electron donor-acceptor dyads to study the relationship between molecular structures and the possibility of charge transfer (CT) and intersystem crossing (ISC). As compared to the previously reported PTZ-AQ dyad with a direct connection of two units via a C-N single bond, the PTZ and AQ units are connected via a p-phenylene or p-biphenylene linker. Conformation restriction is imposed by attaching ortho-methyl groups on the phenylene linker. UV-vis absorption spectra indicate electronic coupling between the PTZ and AQ units in the dyads without conformation restriction. Different from the previously reported PTZ-AQ, thermally activated delayed fluorescence (TADF) is observed for the dyads containing one phenylene linker (PTZ-Ph-AQ and PTZ-PhMe-AQ). The prompt fluorescence lifetime in cyclohexane is exceptionally long (τPF = 62.0 ns, population ratio: 99.2%) and 245.0 ns (93.5%) for PTZ-Ph-AQ and PTZ-PhMe-AQ, respectively (normally τPF <20 ns); the delayed fluorescence lifetimes for these two dyads were determined as τDF = 2.4 μs (6.5%) and 7.6 μs (0.8%), respectively. For the dyad containing a biphenylene linker (PTZ-Ph2Me-AQ), no TADF was observed. Charge-separated (CS) states were observed for PTZ-Ph-AQ and PTZ-PhMe-AQ, and the lifetimes were determined as 7.0 and 1.3 μs, respectively, indicating the triplet spin multiplicity of the CS state. The 3CS state lifetimes are shortened to 100 ns and 440 ns for the two dyads, respectively, in the polar solvent acetonitrile. For dyads with a longer linker, i.e., PTZ-Ph2Me-AQ, the CS state lifetime is not sensitive to solvent polarity (τCS = 1.8 and 1.3 μs in cyclohexane and acetonitrile, respectively). In reference dyads, where the PTZ unit is oxidized to sulfoxide, no CT absorption band and TADF were observed, which is attributed to the increased CS state energy (>3 eV) becoming higher than that of the AQ triplet (3AQ*) state (ca. 2.7 eV). These experimental evidence show that the presence of 1CS, 3CS, and 3LE (LE: locally excited) states sharing similar energy is essential for the occurrence of TADF. Population of the long-lived 3CS state (with a lifetime of a few μs) does not produce by itself TADF, because the ISC process of 1CS→3CS is nonsufficient. Femtosecond transient absorption spectra show that charge separation (CS) occurs readily (<5 ps) for most dyads, even in nonpolar solvents. Nanosecond pulsed laser-excited time-resolved electron paramagnetic resonance (TREPR) spectra show that either a spin correlated radical pair (SCRP) is formed, with the electron exchange energy 2J = +2.14 mT, or radical pairs with stronger interaction, |2J| > 6.57 mT. These studies are useful for in-depth understanding of the CS and ISC in compact electron donor-acceptor dyads and for design of efficient TADF emitters.

Recent Development of Heavy Atom-Free Triplet Photosensitizers for Photodynamic Therapy

Photodynamic therapy (PDT) is an attractive method for cancer treatment. Triplet photosensitizers (PSs) are critical for this method; upon photoexcitation, efficient intersystem crossing (ISC) occurs for triplet PSs, the triplet-excited state of the triplet PSs is populated, then via intermolecular triplet energy transfer, the O2, in triplet-spin multiplicity at ground state, is sensitized to the singlet-excited state, i.e., singlet oxygen (1O2) is produced. This strong reactive oxygen species (ROS) will oxidize the biomolecules in the tumor tissue. Thus, the design of novel triplet PSs as efficient PDT agents is vital. In this review article, we will introduce the recent development of the heavy atom-free triplet PSs used for PDT, including those based on spin-orbit charge transfer ISC (SOCT-ISC), twisting of the π-conjugation framework-induced ISC, radical enhanced ISC, and thionated carbonyl-induced ISC. The ISC mechanisms and molecular structure design rationales are discussed. The less studied electron spin selectivity of the ISC of the triplet PSs is also introduced. This information is helpful for the future design of new efficient triplet PSs for PDT.

Theoretical Rovibrational Spectroscopy of Magnesium Tricarbide-Multireference Character Thwarts a Full Analysis of All Isomers.

Magnesium tricarbide isomers are studied herein with coupled cluster theory and multireference configuration interaction to support their possible detection in astrochemical environments such as the circumstellar envelope surrounding the star IRC +10216 or in terrestrial laboratories. Magnesium-bearing species may abound in the interstellar medium (ISM), but only eight (MgNC, MgCN, HMgNC, MgC2H, MgC3N, MgC4H, MgC5N, and MgC6H) have been directly identified thus far. Several possible isomers for the related MgC3 system are explored in their singlet and triplet spin multiplicities. Overall, this work offers quantum chemical insight of rovibrational spectroscopic data for MgC3 using quartic force fields (QFFs) based on the CCSD(T) and CCSD(T)-F12 levels of theory at the complete basis set (CBS) limit. Additional corrections with small basis set CCSDT(Q) and scalar relativistic effects are also included in the analysis. Salient multireference character is found in the singlet diamond electronic state, which makes a definitive assignment of the ground state challenging. Nevertheless, coupled cluster-based composite energies and multireference configuration interaction both predict that the 1A1 diamond isomer is 1.6-2.2 kcal mol-1 lower in energy than the 3A1 diamond isomer. Furthermore, highly accurate binding energies of various isomers MgC3 are provided for comparison to photodetachment experiments. Dipole moments along with harmonic infrared intensities will guide efforts for astronomical and spectroscopic characterization.

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide.

Phosphorus monoxide (. PO) is a key intermediate in phosphorus chemistry, and its association with the hydroxyl radical (. OH) to yield metaphosphorous acid (cis-HOPO) contributes to the chemiluminescence in the combustion of phosphines. When photolyzing cis-HOPO in an Ar-matrix at 2.8 K, the simplest dioxophosphorane HPO2 and an elusive hydroxyl radical complex (HRC) of . PO form. This prototypical radical-radical complex reforms into cis-HOPO at above 12.0 K by overcoming a barrier of 0.28±0.02 kcal mol-1 . The vibrational spectra of this HRC and its D- and 18 O-isotopologues suggest a structure of . OH⋅⋅⋅OP. , for which a triplet spin multiplicity with a binding energy of -3.20 kcal mol-1 has been computed at the UCCSD(T)-F12a/aug-cc-pVTZ level.

The Triplet Hydroxyl Radical Complex of Phosphorus Monoxide

AbstractPhosphorus monoxide (.PO) is a key intermediate in phosphorus chemistry, and its association with the hydroxyl radical (.OH) to yield metaphosphorous acid (cis‐HOPO) contributes to the chemiluminescence in the combustion of phosphines. When photolyzing cis‐HOPO in an Ar‐matrix at 2.8 K, the simplest dioxophosphorane HPO2 and an elusive hydroxyl radical complex (HRC) of .PO form. This prototypical radical‐radical complex reforms into cis‐HOPO at above 12.0 K by overcoming a barrier of 0.28±0.02 kcal mol−1. The vibrational spectra of this HRC and its D‐ and 18O‐isotopologues suggest a structure of .OH⋅⋅⋅OP., for which a triplet spin multiplicity with a binding energy of −3.20 kcal mol−1 has been computed at the UCCSD(T)‐F12a/aug‐cc‐pVTZ level.

Photochemistry from low-lying states of HOSO.

Using configuration interaction ab initio methods, the evolution of the lowest electronic states of singlet and triplet spin multiplicities of HOSO+ along the stretching and bending coordinates of is investigated. Equilibrium geometries, rotational constants, and harmonic vibrational frequencies of the lowest electronic states are calculated, i.e., X1A', 11A″, 13A', and 13A″. The global minimum of the 11A″ state is located below the first dissociation limit and its calculated lifetime is predicted to be 0.40 µs, making it suitable for detection by laser-induced fluorescence. According to the potential energy surfaces, HOSO+ should produce SO2 + and H after ultraviolet photon absorption to the 21A' state. This work opens the door to investigate the branching ratio and the production rates of SO2 +, SO+, and OH from HOSO+. These insights can help understand the SO2 cycle in the earth's atmosphere and its effect on cooling our planet.

O-H and C-H Bond Activations of Water and Methane by RuO2+ and (NH3)RuO2+: Ground and Excited States.

Investigation of the ground and excited states of RuO2+ is carried out using multireference quantum chemical methodologies. The electronic structure is explored in detail, and accurate spectroscopic constants for 12 states are reported. Although ruthenium belongs to the same group as iron, the ground state of RuO2+ is 1Σ+ with a strong oxo character as opposed to the 3Δ of FeO2+ with primarily oxyl character. To see the effect of the different electronic structure of RuO2+ on the O-H and C-H bond activation processes, we studied its reaction with one water or methane molecule. Reaction energies and activation barriers are given for six low-lying electronic states of singlet, triplet, and quintet spin multiplicities. It is found that the higher-energy quintet state (5Σ+) provides the lowest activation energies and is the same state responsible for the C-H activation for FeO2+ complexes. The reason is attributed to its weaker metal-oxygen bond (longer bond length), which is "prepared" to be activated at the same time with the O-H and C-H bonds. The effect of an ammonia ligand in the chemical activity is also discussed.

Thickness-Dependent Reactivity of O2 on Cu Layers Grown on Ru(0001) Surfaces

The reaction of diatomic molecules on bimetallic surfaces, formed by one to few monolayers of a metal adsorbed on a different metal substrate, is relevant to understand the role of surface strain and substrate chemical binding in catalysis, which is interesting for industrial applications, challenges existing state-of-the-art theoretical methods, due to the additional complexity associated with having a molecule with triplet spin multiplicity. Here, we have studied the interaction of O2 with CuxML/Ru(0001) (x being the number of Cu monolayers), for which experimental data are available, by means of multidimensional classical dynamics simulations based on first-principles potential energy surfaces. Our results show, on the one hand, that the inclusion of the surface temperature on the simulations is essential to reproduce the experimental observations, and therefore, to analyze the physical mechanisms behind these observations, and, on the other hand, that electronic effects due to the binding between the ...

Synthesis of an Iron(IV) Aqua-Oxido Complex Using Ozone as an Oxidant.

The iron(IV) oxido complex [(tmc)Fe=O(OTf)]OTf with the macrocyclic ligand 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclo-tetradecane (tmc) has been synthesized using ozone as an oxidant. By adding water to this compound the complex [(H2 O)(tmc)Fe=O)](OTf)2 could be prepared. This complex is important in regard to a better understanding of the reactivity of FeIV oxido complexes. Mössbauer measurements using the solid compound showed an isomer shift of δ=0.19 mm s-1 and a quadrupole splitting ΔEQ =1.38 mm s-1 , confirming the high-valent FeIV state. DFT calculations were performed and led to an assignment of triplet spin multiplicity. Crystallographic characterization of [(H2 O)(tmc)Fe=O)](OTf)2 as well as of starting materials [(tmc)Fe(CH3 CN)](OTf)2 and [(tmc)Fe(OTf)]OTf together with previous results strongly suggest that [(H2 O)(tmc)Fe=O)](OTf)2 was formed similar to the oxido-hydroxido tautomerism analogous to heme systems.

Synthesis of an Iron(IV) Aqua–Oxido Complex Using Ozone as an Oxidant

AbstractThe iron(IV) oxido complex [(tmc)Fe=O(OTf)]OTf with the macrocyclic ligand 1,4,8,11‐tetramethyl‐1,4,8,11‐tetraazacyclo‐tetradecane (tmc) has been synthesized using ozone as an oxidant. By adding water to this compound the complex [(H2O)(tmc)Fe=O)](OTf)2 could be prepared. This complex is important in regard to a better understanding of the reactivity of FeIV oxido complexes. Mössbauer measurements using the solid compound showed an isomer shift of δ=0.19 mm s−1 and a quadrupole splitting ΔEQ=1.38 mm s−1, confirming the high‐valent FeIV state. DFT calculations were performed and led to an assignment of triplet spin multiplicity. Crystallographic characterization of [(H2O)(tmc)Fe=O)](OTf)2 as well as of starting materials [(tmc)Fe(CH3CN)](OTf)2 and [(tmc)Fe(OTf)]OTf together with previous results strongly suggest that [(H2O)(tmc)Fe=O)](OTf)2 was formed similar to the oxido–hydroxido tautomerism analogous to heme systems.

Excitonic Interfacial Proton-Coupled Electron Transfer Mechanism in the Photocatalytic Oxidation of Methanol to Formaldehyde on TiO2(110).

CH3OH on a single-crystal rutile TiO2(110) surface is a widely studied model system for heterogeneous photocatalysis. Using spin-polarized density functional theory with a hybrid functional (HSE06), we study the photocatalytic oxidation of CH3OH adsorbed at a coordinately unsaturated Ti site as an excited-state process with triplet spin multiplicity. The oxidation to CH2O is stepwise and involves a CH3O intermediate. The first O-H dissociation step follows an excitonic interfacial proton-coupled electron transfer mechanism where the hole-electron (h-e) pair generated during the excitation is bound, and the h is transferred to the adsorbate. The O-H dissociation paths associated with other h-e pairs are unreactive, and the moderate experimental efficiency is due to the different reactivity of the h-e pairs. The excited-state CH3O intermediate further deactivates through a seam of intersection between the ground and excited states. It can follow three different paths, regeneration of adsorbed CH3OH or formation of the ground-state CH3O anion or an adsorbed CH2O radical anion. The third channel corresponds to photochemical CH2O formation from CH3OH, where a single photon induces one electron oxidation and transfer of two protons. These results expand the current view on the photocatalysis of CH3OH on TiO2(110) by highlighting the role of excitons and showing that adsorbed CH3OH may also be an active species in the photocatalytic oxidation to CH2O.

Spin Inversion Phenomenon and Two-State Reactivity Mechanism for Direct Benzene Hydroxylation by V4O10 Cluster.

The direct and selective introduction of hydroxyl group into aromatic compounds remains one of the challenging problems in oxidation chemistry. Keeping in view the reported reactivity of vanadium oxide in C-H activation of saturated hydrocarbons, the study explores the reactivity of neutral V4O10 cluster with benzene through rigorous computations performed within the formalism of density functional theory. Three possible reaction channels for the reactivity of V4O10 cluster with benzene have been deciphered, and comprehensive understanding of all possible mechanistic pathways has been obtained by analysis of all the intermediates and transition states encountered en route. The study provides promising evidence of direct abstraction of hydrogen by terminal oxygen of the cluster via three-centered transition state. The scan of potential energy surfaces for the reactivity of the cluster in its ground (singlet) and first excited (triplet) spin multiplicity states establishes two-state reactivity mechanisms. The spin crossover point has been identified through geometric and thermodynamic parameters, partial charges, and intrinsic reaction coordinate calculations. The study establishes the efficacy of V4O10 cluster species in direct hydroxylation of benzene to phenol.

Electronic structure of NSO(-) and SNO(-) anions: Stability, electron affinity, and spectroscopic properties.

The low-energy electronic states of NSO anion and its SNO isomeric form for the singlet, triplet, and quintet spin multiplicities have been investigated by accurate ab initio approaches and large atomic basis sets. One-dimensional cuts of the three-dimensional potential energy surfaces (PESs) along selected interatomic distances and bending angles for these states have been calculated to assess the formation and stability of NSO(-) and SNO(-) in the gas phase. Results show that these anions have two low-energy states (X̃(1)A(') and 1(3)A″) that are bound and stable with respect to electron detachment. Owing to the energetic position of the dissociating asymptotes of the neutral and anionic species, several electronic excited states are suggested to be stable with respect to the electron autodetachment process in the long-range parts of the potentials before reaching the molecular region. The nature of the PESs in these regions and their implications and effects on the formation of SNO(-) from atomic and molecular fragments are discussed. This information is essential for a better understanding of the potential role of these species in diverse media.

Fused oligothiophene and -selenophene: A DFT insight

Density functional theory calculations were carried out on fused oligothiophenes, their cation radicals and dications (singlet and triplet spin multiplicity) as well as fused polythiophene at B3LYP/6-31G(d) level of theory and compared with their selenophene analogues. The effective conjugation in both the series of fused oligomers was compared on the basis of ‘bond length alternation’ (BLA). Fused oligo- and polyselenophenes have a more quinoidal character and lower band gap (HOMO–LUMO gap) than their thiophene analogues. The band gaps of polymers were obtained by extrapolation of HOMO–LUMO gap versus 1/n. The deviation from 1/n dependence in HOMO–LUMO gaps starts from n⩾31. Thus HOMO–LUMO gaps show convergence behavior. Similar to that of the linear non-fused oligomers of thiophene and selenophene, fused oligothiophene and -selenophene show linear relationship between the internal reorganization energy for self-exchange hole-transfer process (λ) and the square root of chain length only for short oligomers. For longer oligomers, it follows a linear relationship with the reciprocal of chain length and extrapolation gives λ≈0 for polymers. The dications longer than 11-mer showed the RHF/UHF instability and it can be understood as the contribution of the polaron-pair state to the ground-state structure. The calculations suggest that triplet is never a ground state for fused oligothiophene and -selenophene dications. The polaron-pair contribution to the ground state of dication increases with chain length of fused oligothiophene and -selenophene. The triplet state and unrestricted singlet state become degenerate for longer fused oligothiophene and -selenophene, whereas for smaller fused oligomer (up to 20-mer) the singlet state dications are more stable than triplet state dications. The fused oligo- and polythiophene and -selenophene behave similar to the non-fused linear oligo- and polythiophene and -selenophene and do not behave like oligo- and polyacenes.

On the role of the simplest S-nitrosothiol, HSNO, in atmospheric and biological processes

Using state-of-the-art theoretical methods, we investigate the lowest electronic states of singlet and triplet spin multiplicities of HSNO. These computations are done using configuration interaction ab initio methods and the aug-cc-pV5Z basis set. One-dimensional cuts of the six-dimensional potential energy surfaces of these electronic states along the HS, SN stretches and HSN, SNO bending and torsion coordinates are calculated. Several avoided crossings and conical intersections are found. We computed also radiative lifetimes and spin-orbit couplings of these electronic states. Our work shows that the dynamics on these excited states is very complex, and suggest that multi-step mechanisms will populate the ground state via radiationless processes or lead to predissociation or intramolecular isomerization. For instance, these potentials are used to propose mechanisms for the IR, Vis, and UV light-induced cis-trans interconversions of HSNO and reactivity towards HS + NO and H + SNO products. Our findings are in good agreement with previous experimental studies on the photochemistry of HSNO. The atmospheric implication of HSNO is also discussed.

Polymerization Inhibition by Triplet State Absorption for Nanoscale Lithography

In the field of photopolymerization, multi-photon lithography1 stands out as a mask-free tool for fabricating three-dimensional structures inside a photocurable resin that is transparent at the wavelength used. This approach enables a great deal of versatility compared with single photon absorption lithography where the thickness of the polymerized parts is limited by the penetration depth of the light in the resin2 and therefore a layer-by-layer approach is necessary to fabricate 3D structures.3 The possibility of producing 3D, free-standing, and arbitrarily complex architectures opens up novel applications in various research fields, e.g., photonic crystals, metamaterials, and biological scaffold fabrication.4–10

Versatile Behavior of the Fluorophosphinidene Ligand in Iron Carbonyl Chemistry

Fluorophosphinidene (PF) is a versatile ligand found experimentally in the transient species M(CO)(5)(PF) (M = Cr, Mo) as well as the stable cluster Ru(5)(CO)(15)(μ(4)-PF). The PF ligand can function as either a bent two-electron donor or a linear four-electron donor with the former being more common. The mononuclear tetracarbonyl Fe(PF)(CO)(4) is predicted to have a trigonal bipyramidal structure analogous to Fe(CO)(5) but with a bent PF ligand replacing one of the equatorial CO groups. The tricarbonyl Fe(PF)(CO)(3) is predicted to have two low-energy singlet structures, namely, one with a bent PF ligand and a 16-electron iron configuration and the other with a linear PF ligand and the favored 18-electron iron configuration. Low-energy structures of the dicarbonyl Fe(PF)(CO)(2) have bent PF ligands and triplet spin multiplicities. The lowest energy structures of the binuclear Fe(2)(PF)(CO)(8) and Fe(2)(PF)(2)(CO)(7) derivatives are triply bridged structures analogous to the experimental structure of the analogous Fe(2)(CO)(9). The three bridges in each Fe(2)(PF)(CO)(8) and Fe(2)(PF)(2)(CO)(7) structure include all of the PF ligands. Other types of low-energy Fe(2)(PF)(2)(CO)(7) structures include the phosphorus-bridging carbonyl structure (FP)(2)COFe(2)(CO)(6), lying only ~2 kcal/mol above the global minimum, as well as an Fe(2)(CO)(7)(μ-P(2)F(2)) structure in which the two PF groups have coupled to form a difluorodiphosphene ligand unsymmetrically bridging the central Fe(2) unit.

Pump-probe photoelectron velocity-map imaging of autoionizing singly excited4s14p6np1(n=7,8)and doubly excited4s24p45s16p1resonances in atomic krypton

Pump-probe photoelectron velocity-map imaging, using 27-eV high-harmonic excitation and 786-nm ionization, is used to resolve overlapping autoionizing resonances in atomic krypton, obtaining two-photon photoelectron angular distributions (PADs) for singly and doubly excited states. Two features in the photoelectron spectrum are assigned to singly excited 4${s}^{1}$4${p}^{6}$$n{p}^{1}$ ($n$ $=$ 7,8) configurations and four features provide information about double excitation configurations. The anisotropy parameters for the singly excited 7$p$ configuration are measured to be \ensuremath{\beta}${}_{2}$ $=$ 1.61 \ifmmode\pm\else\textpm\fi{} 0.06 and \ensuremath{\beta}${}_{4}$ $=$ 1.54 \ifmmode\pm\else\textpm\fi{} 0.16 while the 8$p$ configuration gives \ensuremath{\beta}${}_{2}$ $=$ 1.23 \ifmmode\pm\else\textpm\fi{} 0.19 and \ensuremath{\beta}${}_{4}$ $=$ 0.60 \ifmmode\pm\else\textpm\fi{} 0.15. These anisotropies most likely represent the sum of overlapping PADs from states of singlet and triplet spin multiplicities. Of the four bands corresponding to ionization of doubly excited states, two are assigned to 4${s}^{2}$4${p}^{4}$5${s}^{1}$6${p}^{1}$ configurations that are probed to different $J$-split ion states. The two remaining doubly excited states are attributed to a previously observed, but unassigned, resonance in the vacuum-ultraviolet photoabsorption spectrum. The PADs from each of the double excitation states are also influenced by overlap from neighboring states that are not completely spectrally resolved. The anisotropies of the observed double excitation states are reported, anticipating future theoretical and experimental work to separate the overlapping PADs into the state resolved PADs. The results can be used to test theories of excited state ionization.