Closed-shell Cations Research Articles

Lewis Acid-Base Pairs: The Bonding Rule of Closed-Shell M···M' Interactions (M = HgII/PdII; M' = AgI/AuI).

Metallophilic interactions are the widespread interactions in multimetal clusters to orientate closed-shell metal self-assembly form linear, facet, or block clusters. The closed-shell metal cation does not have empty valence orbitals, but is able to attract each other. It is still a conundrum to understand the resource in balancing the strong Coulomb repulsion between two cations. Most traditional descriptions attribute the counterintuitive attractions to London dispersion, Pauli repulsions, and ambiguous orbital interactions. However, neither the dispersion nor the unsourced donor-acceptor interaction can be applied to explain the saturability and directionality in multimetal clusters, where the M···M' structure is the basic molecular unit. Here, we clarify the origination of the covalency in closed-shell metallophilic interactions based on the study of heterobimetallic compounds composed of d10-d8 species (AgI/AuI-PdII) and d10-d10 species (AgI/AuI-HgII) obtained from experiments. The inner d electrons not only participate in the metallophilic interactions but also show different Lewis acidity and basicity in the formation of M···M' structures. The present work not only provides us a novel covalent perspective to visualize the closed-shell M···M' interactions but also unveils the truth of metallophilic interactions.

Unprecedented intact radical anions, closed shell anions, cluster ions, and traditional cations and radical cations by LIFDI-MS.

Liquid injection field desorption ionization (LIFDI) proves the extraordinary softness of the ionization process combined with a convenient sample supply under the exclusion of moisture and air. LIFDI-mass spectrometry (MS) is used for organometallic and other seriously air-sensitive compounds forming intact ions without substantial fragmentation. Unprecedented molecular radical anions M-• are presented along with well-known intact M+• radical cations. Furthermore closed shell cations [C]+ and adduct ions like [M + H]+ or [M + Alkali]+ are gently transferred from the solid emitter surface into the gas phase. Anions [A]- or [M - H]- are accessible by LIFDI-MS at medium field strengths. Ion pairs [C]+[A]- are separately detected by positive and negative mode LIFDI-MS, respectively. Here we give an overview of the different ion types accessible by LIFDI-MS. For the first time the field ionization/desorption of solar cell electron acceptor compounds is shown to deliver M-• and M2-• radical ions.

Bimetallic superalkali substitution in the CsPbBr3 perovskite: Pseudocubic phases and tunable bandgap.

Perovskites attract attention as efficient light absorbers for solar cells due to their high-power conversion efficiency (up to 24%). The high photoelectric conversion efficiency is greatly affected by a suitable band structure. Cation substitution can be an effective approach to tune the electronic band structure of lead halide perovskites. In this work, superalkali cations were introduced to replace the Cs+ cation in the CsPbBr3 material. The bimetallic superalkalis (LiMg, NaMg, LiCa, and NaCa) were inserted since they are structurally simple systems and have a strong tendency to lose one electron to achieve a closed-shell cation. The cation substitution in the lead halide perovskite leads to changes in the shape of both valence and conduction bands compared to CsPbBr3. Introducing superalkali cations produces extra electronic states close to the Fermi level, which arise from the formation of alkali earth metal states at the top of the valence band. Our first-principles computations reveal that bimetallic superalkali substitution decreases the bandgap of the perovskite. The bandgaps of MgLi-PbBr3 (1.35eV) and MgNa-PbBr3 (1.06eV) are lower than the bandgap of CsPbBr3 (2.48eV) and within the optimal bandgap (i.e., 1.1-1.4eV) for single-junction solar cells. Thus, the MgLi-PbBr3 and MgNa-PbBr3 inorganic perovskites are promising candidates for high-efficiency solar cells.

Chemical Reduction of NiII Cyclam and Characterization of Isolated NiI Cyclam with Cryogenic Vibrational Spectroscopy and Inert-Gas-Mediated High-Resolution Mass Spectrometry.

NiII cyclam (cyclam = 1,4,8,11-tetraazacyclotetradecane) is an efficient catalyst for the selective reduction of CO2 to CO. A crucial elementary step in the proposed catalytic cycle is the coordination of CO2 to a NiI cyclam intermediate. Isolation and spectroscopic characterization of this labile NiI species without solvent has proven to be challenging, however, and only partial IR spectra have previously been reported using multiple photon fragmentation of ions generated by gas-phase electron transfer to the NiII cyclam dication at 300 K. Here, we report a chemical reduction method that efficiently prepares NiI cyclam in solution. This enables the NiI complex to be transferred into a cryogenic photofragmentation mass spectrometer using inert-gas-mediated electrospray ionization. The vibrational spectra of the 30 K ion using both H2 and N2 messenger tagging over the range 800-4000 cm-1 were then measured. The resulting spectra were analyzed with the aid of electronic structure calculations, which show strong method dependence in predicted band positions and small molecule activation. The conformational changes of the cyclam ligand induced by binding of the open shell NiI cation were compared with those caused by the spherical, closed-shell LiI cation, which has a similar ionic radius. We also report the vibrational spectrum of a NiI cyclam complex with a strongly bound O2 ligand. The cyclam ligand supporting this species exhibits a large conformational change compared to the complexes with weakly bound N2 and H2, which is likely due to significant charge transfer from Ni to the coordinated O2.

Approximate equation-of-motion coupled-cluster methods for electron affinities of closed-shell molecules.

We investigate performance of the equation-of-motion coupled-cluster method at the single and doubles level (EOM-CCSD) and a series of approximate methods based on EOM-CCSD on electron affinities (EA) of closed-shell cations and neutral molecules with positive and negative EAs in this work. Our results confirm that P-EOM-MBPT2 can provide reasonable EAs when molecules with significant multireference character are not considered and its mean absolute error on EAs of these molecules is around or less than 0.2 eV. Its accuracy is comparable to that of the more expensive EOM-CCSD(2) method. Results of EOM-CCSD(2), P-EOM-MBPT2, and CIS(D∞) indicate that the [[H, ac +], T2] term in the 1h2p-1h block is more important on EAs than the term neglected in the 1h2p-1h2p block in P-EOM-MBPT2. We proposed an economical method where EAs from CIS(D∞) are corrected by treating this [[H, ac +], T2] term in the 1h2p-1h block perturbatively [corr-CIS(D∞)]. EAs with corr-CIS(D∞) agree very well with those of P-EOM-MBPT2 with a difference of less than 0.02 eV. Computational scaling of this method is N4 for the iterative part and N5 for some non-iterative steps. Its storage requirement is only of OV3. Corr-CIS(D∞) is an economical and reliable method on EAs, and it can be applied to EAs of large molecules.

Double Rydberg anions with solvated ammonium kernels: Electron binding energies and Dyson orbitals

Ab initio electron-propagator calculations on the electron detachment energies and associated Dyson orbitals of NnH3n+1− for n = 1–5 confirm the assignment of low-energy peaks in anion photoelectron spectra to double Rydberg anions, species in which a closed-shell cation binds a diffuse pair of electrons. The most stable double Rydberg anions contain NnH3n+1+ cores, wherein the NH4+ kernel forms n − 1 hydrogen bonds with ammonia molecules. Other low-energy peaks for a given n pertain to double Rydberg anions of lower n that are weakly bound to ammonia molecules. High-energy peaks arise from the most stable isomers which consist of hydrides bound to N–H bonds of coordinating ammonia molecules. Dyson orbitals of electron detachment are distributed over the periphery of the bonding regions of the NnH3n+1+ cores. For n = 2–4, negative charge accumulates mostly outside the N–H bonds of the NH4+ kernels that are not engaged in hydrogen bonds. For the tetrahedral cases, where n = 1, 5, Dyson orbitals are diffuse, symmetric functions that are orthogonalized to occupied a1 orbitals of the cationic core. Shake-up features in spectra have been assigned to doublet states with a single diffuse electron in an s, p, d, or f orbital.

Conjugated Polyions Enable Organic Photovoltaics Processed from Green Solvents

This paper describes the design, synthesis, and optical and electronic properties of two conjugated polymers CPIZ-B and CPIZ-T that incorporate closed-shell cations into their conjugated backbones, balanced by anionic pendant groups. The zwitterionic nature of the polymers renders them soluble in and processable from polar, protic solvents to form semiconducting films that are not doped. These unique properties are confirmed by absorption and electron paramagnetic resonance spectroscopy. The energies of the unoccupied states respond to the tritylium moieties in the conjugated backbone, while the occupied states respond to the electron-donating ability of the uncharged, aromatic units in the backbone. Films cast from 80:20 HCOOH/H2O by volume show good electron mobilities, enabling a photovoltaic effect in proof-of-concept, bilayer solar cells.

In My Element: How did I land in a gold mine?

The In My Element series celebrates the personal accounts from Chemistry – A European Journal Editorial Board members for the 2019 International Year of the Periodic Table. In this contribution, Pekka Pyykkö gives his story on gold. In late 1975 Jean-Paul Desclaux and I had developed a fully relativistic (or non-relativistic) quantum chemical approach for hydride molecules, MHn. It converged well at short M−H bond lengths so we needed a molecule in which that was indeed the case. It turned out that AuH was one, so we tried it and it worked. There was a sizable relativistic contraction of the Au−H bond length. Moreover, relativistic effects explained most of the differences from AgH to AuH. We had the audacity to say that “the chemical difference between silver and gold may mainly be a relativistic effect”1 (see Figure 1). Earlier band-structure studies on Au metal had indicated large relativistic effects2 but in a germ, there may have been a trace of originality in our coupling of chemical periodicity to relativity. That turned out to be a scientific gold mine. Because the shell structure of gold has a local maximum of valence-shell relativistic effects, which normally scale as Z2, that was a lucky start. The relativistic (R) and non-relativistic (NR) orbital energies of the diatomic AgH and AuH (a.u. is atomic units). Data from Ref. 1. Figure from Ref. 17. A decade later, when lecturing at the Technical University of Munich, I learned from Hubert Schmidbaur about a strange attraction between two or more closed-shell AuI cations.3 They had both crystallographic and NMR evidence for it. Both cations carried a positive charge and had no open-shell electrons to make covalent bonds with. Yet they enjoyed an “aurophilic attraction” comparable in strength with a good hydrogen bond. Our explanation for it was a dispersion-type van der Waals interaction.4 Although other mechanisms also may contribute, for example electrostatic multipole interactions or induction,5-7 this is at least a partial explanation. That dispersion-type interaction is also comparable for silver,8, 9 and thus not specific for gold. We are not aware of a known case in which a suggested 6s–6p–5d hybridization10 would be sufficient to yield an observable attraction. Moreover, certain main-group elements also show it. Not only is gold a laboratory of relativistic quantum chemistry. Also, quantum electrodynamic (QED) effects can be seen in the ionization potential and electron affinity of the Au atom by pushing the current theories to their limits.11 Predicting new species with Au was a third aspect. Two examples were the first noble-metal−noble-gas bond12 in AuXe+, observed in mass-spectroscopy, or the predicted nanocluster WAu12,13 also subsequently made.14 Among novel covalent bonds, take the newly prepared unbridged AuII−AuII bonds.15 Both homogeneous and heterogeneous catalysis involving gold have become vast fields. Partially inspired by this application, the studies of both naked and ligand-covered gold nanoclusters are being intensively studied.16 Thus, keeping an eye on the theoretical chemistry of gold is a very good idea.17-20 Position Professor Emeritus of Chemistry E-mail [email protected] Homepage www.chem.helsinki.fi/∼pyykko ORCID 0000-0003-1395-8712 Education University of Turku, Finland, M.Sc. 1964, Ph.D. 1967. Post-doc at Aarhus, Denmark 1968–69 Post-doc at Gothenburg, Sweden 1969–70 Awards A.I. Virtanen Prize 1997, E.J. Nyström Prize 1998 decorated by President of Finland (FVR R I, 1995) Humboldt Prize 2002, Palmes Académiques (France) 2009 Schrödinger medal 2012 Honorary Fellow of Chinese Chemical Society 2012 Research interests Quantum chemistry of heavy elements Recently: simple models for eutectics

Exploring Closed-Shell Cationic Phenalenyl: From Catalysis to Spin Electronics.

The odd alternant hydrocarbon phenalenyl (PLY) can exist in three different forms, a closed-shell cation, an open-shell radical, and a closed-shell anion, using its nonbonding molecular orbital (NBMO). The chemistry of PLY-based molecules began more than five decades ago, and so far, the progress has mainly involved the open-shell neutral radical state. Over the last two decades, we have witnessed the evolution of a range of PLY-based radicals generating an array of multifunctional materials. However, it has been admitted that the practical applications of PLY radicals are greatly challenged by the low stability of the open-shell (radical) state. Recently, we took a different route to establish the utility of these PLY molecules using the closed-shell cationic state. In such a design, the closed-shell unit of PLY can readily accept free electrons, stabilizing in its NBMO upon generation of the open-shell state of the molecule. Thus, one can synthetically avoid the unstable open-shell state but still take advantage of this state by in situ generating the radical through external electron transfer or spin injection into the empty NBMO. It is worth noting that such approaches using closed-shell phenalenyl have been missing in the literature. This Account focuses on our recent developments using the closed-shell cationic state of the PLY molecule and its application in broad multidisciplinary areas spanning from catalysis to spin electronics. We describe how this concept has been utilized to develop a variety of homogeneous catalysts. For example, this concept was used in designing an iron(III) PLY-based electrocatalyst for a single-compartment H2O2 fuel cell, which delivered the best electrocatalytic activity among previously reported iron complexes, organometallic catalysts for various homogeneous organic transformations (hydroamination and polymerization), an organic Lewis acid catalyst for the ring opening of epoxides, and transition-metal-free C-H functionalization catalysts. Moreover, this concept of using the empty NBMO present in the closed-shell cationic state of the PLY moiety to capture electron(s) was further extended to an entirely different area of spin electronics to design a PLY-based spin-memory device, which worked by a spin-filtration mechanism using an organozinc compound based on a PLY backbone deposited over a ferromagnetic substrate. In this Account, we summarize our recent efforts to understand how this unexplored closed-shell state of the phenalenyl molecule, which has been known for over five decades, can be utilized in devising an array of materials that not only are important from an organometallic chemistry or organic chemistry point of view but also provide new understanding for device physics.

Photoabsorption in sodium clusters: first principles configuration interaction calculations

We present systematic and comprehensive correlated-electron calculations of the linear photoabsorption spectra of small neutral closed- and open-shell sodium clusters (Na_{n}, n=2-6), as well as closed-shell cation clusters (Na_{n}^{+}, n=3, 5). We have employed the configuration interaction (CI) methodology at the full CI (FCI) and quadruple CI (QCI) levels to compute the ground, and the low-lying excited states of the clusters. For most clusters, besides the minimum energy structures, we also consider their energetically close isomers. The photoabsorption spectra were computed under the electric-dipole approximation, employing the dipole-matrix elements connecting the ground state with the excited states of each isomer. Our calculations were tested rigorously for convergence with respect to the basis set, as well as with respect to the size of the active orbital space employed in the CI calculations. These calculations reveal that as far as electron-correlation effects are concerned, core excitations play an important role in determining the optimized ground state geometries of various clusters, thereby requiring all-electron correlated calculations. But, when it comes to low-lying optical excitations, only valence electron correlation effects play an important role, and excellent agreement with the experimental results is obtained within the frozen-core approximation. For the case of Na_{6}, the largest cluster studied in this work, we also discuss the possibility of occurrence of plasmonic resonance in the optical absorption spectrum.

BREAKDOWN PRODUCTS OF GASEOUS POLYCYCLIC AROMATIC HYDROCARBONS INVESTIGATED WITH INFRARED ION SPECTROSCOPY

ABSTRACT We report on a common fragment ion formed during the electron-ionization-induced fragmentation of three different three-ring polycyclic aromatic hydrocarbons (PAHs), fluorene (C13H10), 9,10-dihydrophenanthrene (C14H12), and 9,10-dihydroanthracene (C14H12). The infrared spectra of the mass-isolated product ions with m/z = 165 were obtained in a Fourier transform ion cyclotron resonance mass spectrometer whose cell was placed inside the optical cavity of an infrared free-electron laser, thus providing the high photon fluence required for efficient infrared multiple-photon dissociation. The infrared spectra of the m/z = 165 species generated from the three different precursors were found to be similar, suggesting the formation of a single isomer. Theoretical calculations using density functional theory (DFT) revealed the fragment's identity as the closed-shell fluorenyl cation. Decomposition pathways from each parent precursor to the fluorenyl ion are proposed on the basis of DFT calculations. The identification of a single fragmentation product from three different PAHs supports the notion of the existence of common decomposition pathways of PAHs in general and can aid in understanding the fragmentation chemistry of astronomical PAH species.

The sequence to hydrogenate coronene cations: A journey guided by magic numbers.

The understanding of hydrogen attachment to carbonaceous surfaces is essential to a wide variety of research fields and technologies such as hydrogen storage for transportation, precise localization of hydrogen in electronic devices and the formation of cosmic H2. For coronene cations as prototypical Polycyclic Aromatic Hydrocarbon (PAH) molecules, the existence of magic numbers upon hydrogenation was uncovered experimentally. Quantum chemistry calculations show that hydrogenation follows a site-specific sequence leading to the appearance of cations having 5, 11, or 17 hydrogen atoms attached, exactly the magic numbers found in the experiments. For these closed-shell cations, further hydrogenation requires appreciable structural changes associated with a high transition barrier. Controlling specific hydrogenation pathways would provide the possibility to tune the location of hydrogen attachment and the stability of the system. The sequence to hydrogenate PAHs, leading to PAHs with magic numbers of H atoms attached, provides clues to understand that carbon in space is mostly aromatic and partially aliphatic in PAHs. PAH hydrogenation is fundamental to assess the contribution of PAHs to the formation of cosmic H2.

Electron-impact excitation of diatomic hydride cations – I. HeH+, CH+, ArH+

{\bf R}-matrix calculations combined with the adiabatic nuclei approximation are used to compute electron-impact rotiational excitation rates for three closed-shell diatomic cations, HeH$^+$, CH$^+$, ArH$^+$. Comparisons with previous studies show that an improved treatment of threshold effects leads to significant changes in the low temperature rates, furthermore the new calculations suggest that excitation of CH$^+$ is dominated by $\Delta J =1$ transitions as is expected for cations with a large dipole moment. A model for ArH$^+$ excitation in the Crab Nebula is presented which gives results consistent with the observations for electron densities in the range $2-3\times 10^3$~cm$^{-3}$.

A new LiNbO3-type polar oxide with closed-shell cations: ZnPbO3

A new lithium-niobate (LiNbO3)-type polar compound, namely, ZnPbO3 (a = 5.41605(7) Å and c = 14.33151(3) Å), with closed-shell ions only was synthesized under high pressure and high temperature (8 GPa and 1273 K). A point-charge-model calculation based on atomic positions refined by Rietveld analysis of synchrotron X-ray diffraction data gave an electrical ionic polarization of 77 μC/cm2 along the hexagonal c-axis. Detailed structural analysis indicated that the contribution of Pb4+ in ZnPbO3 to the polarization was almost twice as large as that of Sn4+ in ZnSnO3. Transport measurement showed metallic behavior of ZnPbO3 from room temperature to low temperature despite the fact that both cations are closed-shell ions.

Testing Noncollinear Spin-Flip, Collinear Spin-Flip, and Conventional Time-Dependent Density Functional Theory for Predicting Electronic Excitation Energies of Closed-Shell Atoms.

Conventional time-dependent density functional theory (TDDFT) is based on a closed-shell Kohn-Sham (KS) singlet ground state with the adiabatic approximation, using either linear response (KS-LR) or the Tamm-Dancoff approximation (KS-TDA); these methods can only directly predict singly excited states. This deficiency can be overcome by using a triplet state as the reference in the KS-TDA approximation and "exciting" the singlet by a spin flip (SF) from the triplet; this is the method suggested by Krylov and co-workers, and we abbreviate this procedure as SF-KS-TDA. SF-KS-TDA can be applied either with the original collinear kernel of Krylov and co-workers or with a noncollinear kernel, as suggested by Wang and Ziegler. The SF-KS-TDA method does bring some new practical difficulties into play, but it can at least formally model doubly excited states and states with double-excitation character, so it might be more useful than conventional TDDFT (both KS-LR and KS-TDA) for photochemistry if these additional difficulties can be surmounted and if it is accurate with existing approximate exchange-correlation functionals. In the present work, we carried out calculations specifically designed to understand better the accuracy and limitations of the conventional TDDFT and SF-KS-TDA methods; we did this by studying closed-shell atoms and closed-shell monatomic cations because they provide a simple but challenging testing ground for what we might expect in studying the photochemistry of molecules with closed-shell ground states. To test their accuracy, we applied conventional KS-LR and KS-TDA and 18 versions of SF-KS-TDA (nine collinear and nine noncollinear) to the same set of vertical excitation energies (including both Rydberg and valence excitations) of Be, B(+), Ne, Na(+), Mg, and Al(+). We did this for 10 exchange-correlation functionals of various types, both local and nonlocal. We found that the GVWN5 and M06 functionals with nonlocal kernels in spin-flip calculations can both have accuracy competitive to CASPT2 calculations. When the results were averaged over all 36 test energy differences, seven (GVWN5, M06, B3PW91, LRC-ωPBE, LRC-ωPBEh, PBE, and M06-2X) of the 10 studied density functionals had smaller mean unsigned errors for noncollinear calculations than the mean unsigned error of the best functional (M06-2X) for either conventional KS-TDA or KS-LR.

Carbocations Generated under Stable Conditions by Ionization of Matrix-Isolated Radicals: The Allyl and Benzyl Cations

Carbocations are crucial intermediates in many chemical reactions; hence, considerable effort has gone into investigating their structures and properties, for example, in superacids, in salts, or in the gas phase. However, studies of the vibrational structure of carbocations are not abundant, because their infrared spectra are difficult to obtain in superacids or salts (where furthermore the cations may be perturbed by counterions), and the generation of gas-phase carbocations in discharges usually produces several species. We have applied the technique of ionizing neutral compounds by X-irradiation of cryogenic Ar matrices to radicals embedded in such matrices, thus producing closed-shell cations that can be investigated leisurely, and in the absence of counterions or other perturbing effects, by various forms of spectroscopy. This Article describes the first set of results that were obtained by this approach, the IR spectra of the allyl and the benzyl cation. We use the information obtained in this way, together with previously obtained data, to assess the changes in chemical bonding between the allyl and benzyl radicals and cations, respectively.

Aromaticity of Closed-Shell Charged Polybenzenoid Hydrocarbons

The aromatic stabilization of closed-shell charged polybenzenoid hydrocarbons (PBHs) has been scrutinized by means of energetic and magnetic aromaticity criteria and by direct measures of electron delocalization. Thus, topological resonance energies and their circuit contributions, ring current maps, and multicenter delocalization indices have been calculated for a series of 18 polybenzenoid cations containing from 3 to 10 benzene rings. All calculations indicate that the closed-shell cations have a similar degree of aromaticity compared to that of the corresponding closed-shell neutral PBHs. All cations investigated display a large degree of electronic delocalization in the ring, accompanied by significant aromatic stabilization and a strong diatropic peripheral electron current. Graph theoretical models describe perfectly the aromatic features of these hydrocarbon fragments, showing how they can be understood as a superposition of specific neutral PBHs. The large aromatic character of these systems suggests they may be relatively stable upon formation at combustion conditions, like those given in the interstellar medium. It has been postulated that closed-shell fragments of PBHs may play an important role in the photoluminescent phenomenon known as extended red emission.

Molecular Photoconductor with Simultaneously Photocontrollable Localized Spins

UV irradiation reversibly switches a new insulating and nonmagnetic molecular crystal, BPY[Ni(dmit)(2)](2) (BPY = N,N'-ethylene-2,2'-bipyridinium; Ni(dmit)(2) = bis(1,3-dithiole-2-thione-4,5-dithiolato)nickelate(III)), into a magnetic conductor. This is possible because the bipyridyl derivative cations (BPY(2+)) trigger a photochemical redox reaction in the crystal to produce a change of ∼10% in the filling of the Ni(dmit)(2) valence band, leaving localized spins on the BPY themselves. In the dark, almost all of the BPY molecules are closed-shell cations, and most of the Ni(dmit)(2) radical anions form spin-singlet pairs; thus, this material is a diamagnetic semiconductor. Under UV irradiation, a photocurrent is observed, which enhances the conductivity by 1 order of magnitude. Electron spin resonance measurements indicate that the UV irradiation reversibly generates carriers and localized spins on the Ni(dmit)(2) and the BPY, respectively. This high photoconductivity can be explained by charge transfer (CT) transitions between Ni(dmit)(2) and BPY in the UV region. In other words, the photoconduction and "photomagnetism" can be described as reversible optical control of the electronic states between an ionic salt (BPY(2+)/[Ni(dmit)(2)](-), nonmagnetic insulator) and a CT complex (BPY(2(1-δ)+)/[Ni(dmit)(2)]((1-δ)-) (δ ≈ 0.1), magnetic conductor) in the solid state.

On the electronic spectroscopy of closed-shell cations derived from resonance-stabilized radicals: Insights from theory and Franck-Condon analysis

Author Institution: School of Chemistry, The University of Sydney, NSW 2006, Australia; Department of Chemistry, Marquette University, Milwaukee, WI 53233

ELECTRONIC SPECTROSCOPY OF FUV-IRRADIATED DIAMONDOIDS: A COMBINED EXPERIMENTAL AND THEORETICAL STUDY

Irradiation with high energy photons (10.2 - 11.8 eV) was applied to small diamondoids isolated in solid rare gas matrices at low temperature. The photoproducts were traced via UV absorption spectroscopy. We found that upon ionization the smallest of these species lose a peripheral H atom to form a stable closed-shell cation. This process is also likely to occur under astrophysical conditions for gas phase diamondoids and it opens the possibility to detect diamond-like molecules using their rotational spectrum since the dehydrogenated cations possess strong permanent dipole moments. The lowest-energy electronic features of these species in the UV were found to be rather broad, shifting to longer wavelengths with increasing molecular size. Calculations using time-dependent density functional theory support our experimental findings and extend the absorption curves further into the vacuum ultraviolet. The complete sigma - sigma* spectrum displays surprisingly strong similarities to meteoritic nanodiamonds containing 50 times more C atoms.