Neon Matrices Research Articles

Wasserstoffaktivierung mit Phenylradikal durch Protium‐ und Deuteriumtunneln

AbstractDie Aktivierung von molekularem Wasserstoff, H2, ist eine herausfordernde Aufgabe, die vorwiegend mithilfe von Übergangsmetallzentren in Angriff genommen wird. Reine Hauptgruppenverbindungen, die dazu in der Lage sind, wurden erst in den letzten Jahrzehnten entwickelt. Solche Verbindungen nutzen synergistische Donor‐Akzeptor‐Wechselwirkungen mit dem antibindenden σ*‐ und dem bindenden σ‐Orbital von H2. Eine alternative, radikalvermittelte Aktivierung ist problematisch, da die H−H‐Bindung stärker ist (104,2 kcal mol−1) als die meisten C−H‐Bindungen. Hier nutzen wir das Phenylradikal, um dieses Problem zu lösen, wobei Benzol mit einer C−H‐Bindungsenergie von 112,9 kcal mol−1 entsteht, wodurch eine thermodynamische Triebkraft erzeugt wird. Bei der Photolyse von Iodbenzol in einer H2‐dotierten Neonmatrix bei 4,4 K beobachten wir trotz einer Reaktionsbarriere von 7,6 kcal mol−1 hauptsächlich die Bildung eines Benzol‐HI‐Komplexes, während im Fall des schwereren D2‐Isotopologs das Phenylradikal entsteht. Wenn die D2‐Moleküle diffundieren können, bildet sich monodeuteriertes Benzol innerhalb von Stunden. Pfadintegralbasierte Instanton‐ Rechnungen ergeben, dass sich bei der Reaktion vorwiegend das transferierte Wasserstoffatom bewegt, was die Tunnelwahrscheinlichkeit stark erhöht. In guter Übereinstimmung mit dem Experiment sagen wir signifikante Reaktionsgeschwindigkeiten für beide Isotope, H2 und D2, voraus sowie einen ausgeprägten kinetischen Isotopeneffekt von bis zu vier Größenordnungen bei tiefsten Temperaturen.

Phenyl Radical Activates Molecular Hydrogen Through Protium and Deuterium Tunneling.

Activating dihydrogen, H2, is a challenging endeavor typically achieved using transition metal centers. Pure main-group compounds capable of this are rare and have emerged in recent decades. These systems rely on synergistic donor-acceptor interactions with H2's antibonding σ* and bonding σ orbital. An alternative (hydrocarbon) radical-mediated activation is problematic because the H-H bond is stronger (104.2 kcal mol-1) than most C-H bonds. Here, we explore using the phenyl radical to tackle this, forming benzene with a C-H bond energy (112.9 kcal mol-1) that provides a thermodynamic driving force. We mainly observe a benzene-HI complex upon photolysis of iodobenzene in an H2-doped neon matrix at 4.4 K despite a barrier of 7.6 kcal mol-1, while phenyl radical forms in case of the heavier D2 isotopologue. When D2 molecules are allowed to diffuse, mono-deuterated benzene accumulates within hours. Computations using path integral-based instanton theory highlight that primarily the transferred hydrogen atom is moving during the reaction which greatly increases the tunneling probability. In excellent agreement with the experimental results, we predict significant tunneling rate constants for both isotopologues, H2 and D2, featuring a strong kinetic isotope effect of up to four orders of magnitude at the lowest temperatures.

How Vibrational Notations Can Spoil Infrared Spectroscopy: A Case Study on Isolated Methanol.

Unraveling methanol's infrared spectrum has challenged spectroscopists for a century, with numerous loose ends still to be explored. We engage in this exploration based on experiments of isolating single methanol molecules in solid argon and neon matrices. We report infrared spectra of methanol in its natural isotopic composition and with partial and full deuteration. These experiments are accompanied by calculating wavenumbers involving anharmonicity and mode-coupling based on the vibrational configuration interaction approach. This allows for an unambiguous assignment of all fundamentals and resonances in the mid-infrared spectrum. An increasing degree of deuteration lifts resonances and aids in assigning bands uniquely. It also becomes evident that different notations typically used in chemistry or physics to describe molecular vibration from spectroscopy fail to describe the spectra appropriately. We highlight the shortcomings and suggest a more elaborate analysis using Sankey diagrams to unambiguously identify spectral features. Consequently, we demystify debated resonances occurring from various stretches and deformations of the methyl group.

Heavy-Atom Tunneling in Ring-Closure Reactions of Beryllium Ozonide Complexes.

Quantum mechanical tunneling (QMT) has long been recognized as crucial for understanding chemical reaction mechanisms, particularly in reactions involving light atoms like hydrogen. However, recent findings have expanded this understanding to include heavy-atom tunneling reactions. In this report, we present the observation of two heavy-atom tunneling reactions involving the spontaneous conversions from end-on bonded beryllium ozonide complexes, OBeOOO (A) and BeOBeOOO (C), to their corresponding side-on bonded ozonide isomers, OBe(η2-O3) (B) and BeOBe(η2-O3) (D), respectively, in a cryogenic neon matrix. This discovery is supported by the weak temperature dependence of the rate constants and unusually large 16O/18O kinetic isotope effects. Quantum chemistry calculations reveal extremely low barriers (<1 kcal/mol) for both ring-closure reactions. Additionally, instanton theory calculations on both reactions unveil that the tunneling processes involve the concerted motion of all four oxygen atoms.

Regularities and Anomalies in Neon Matrix Shifts of Hydrogen-Bonded O-H Stretching Fundamentals.

O-H bond stretching vibrations in hydrogen-bonded complexes embedded into cryogenic neon matrices are subtly downshifted from cold gas phase reference wavenumbers. To the extent that this shift is systematic, it enables neon matrices as more universally applicable spectroscopic benchmark environments for quantum chemical predictions. Outliers are indicative of either an assignment problem in one of the two cryogenic experiments or they reveal interesting dynamics or structural effects on the complexes as a function of the environment. We compile 6 literature-known pairs of experimental data in jet and neon matrix expansions and realize a 6-fold expansion of that number through targeted matrix isolation and/or slit jet expansion spectroscopy presented in this work. In many cases, the neon matrix shift is less than the uncertainty of the currently best-performing blind quantum chemical predictions for the gas phase, but in specific cases, it may exceed the currently achievable theoretical accuracy. Some evidence for a positive correlation of the matrix shift with the hydrogen bond shift is found, similar to observations for helium nanodroplets. Outliers in particular for water acting as a donor are discussed, and in a few cases they call for a future reinvestigation. Substantial improvement in the correlation of the matrix shift with the hydrogen bond shift is achieved for ketone monohydrates by removing a vibrational resonance. New insights into nitrile hydration isomerism are obtained, and the linear OH stretching spectrum of the jet-cooled ammonia-water complex is presented for the first time. Vibrational spectroscopy in weakly perturbing solid rare gas quantum matrices for the benchmarking of gas phase theory and future explicit theoretical treatments of the quantum matrix environment to better understand the outliers are both encouraged.

Acriflavine Is More than It Seems: Resolving Optical Properties of Multiple Isomeric Constituents at 5 K.

Ion mobility spectrometry at room temperature was combined with vibrationally resolved electronic spectroscopy of mass-selected ions at 5 K to study the well-known cationic fluorophore acriflavine. One- and two-color photodepletion action spectra recorded in gas-phase (by helium tagging) as well as dispersed fluorescence spectra obtained in neon matrix (after soft-landing deposition) indicate that the primary cation mass electrosprayed from solution comprises two isomers with different optical properties. Theory at the TD-DFT level allowed full spectral assignment. The results have implications for the preparation of novel thin film photonic materials by low-energy ion beam deposition.

Investigation of Isolated IrF5 -, IrF6 - Anions and M[IrF6] (M=Na, K, Rb, Cs) Ion Pairs by Matrix-Isolation Spectroscopy and Relativistic Quantum-Chemical Calculations.

The molecular IrF5 -, IrF6 - anions and M[IrF6] (M=Na, K, Rb, Cs) ion pairs were prepared by co-deposition of laser-ablated alkali metal fluorides MF with IrF6 and isolated in solid neon or argon matrices under cryogenic conditions. The free anions were obtained as well by co-deposition of IrF6 with laser-ablated metals (Ir or Pt) as electron sources. The products were characterized in a combined analysis of matrix IR spectroscopy and electronic structure calculations using two-component quasi-relativistic DFT methods accounting for spin-orbit coupling (SOC) effects as well as multi-reference configuration-interaction (MRCI) approaches with SOC. Inclusion of SOC is crucial in the prediction of spectra and properties of IrF6 - and its alkali-metal ion pairs. The observed IR bands and the computations show that the IrF6 - anion adopts an Oh structure in a nondegenerate ground state stabilized by SOC effects, and not a distorted D4h structure in a triplet ground state as suggested by scalar-relativistic calculations. The corresponding "closed-shell" M[IrF6] ion pairs with C3v symmetry are stabilized by coordination of an alkali metal ion to three F atoms, and their structural change in the series from M=Na to Cs was proven spectroscopically. There is no evidence for the formation of IrF7, IrF7 - or M[IrF7] (M=Na, K, Rb, Cs) ion pairs in our experiments.

Spectroscopic Identification of Trifluorosilylphosphinidene and Isomeric Phosphasilene and Silicon Trifluorophosphine Complex.

The perfluorinated silylphosphinidene, F3SiP, in the triplet ground state is generated by the reaction of laser-ablated silicon atoms with PF3 in solid neon and argon matrices. The reactions proceed with the initial formation of a silicon trifluorophosphine complex, F3PSi, in the triplet ground state, and a more stable inserted phosphasilene, FPSiF2, in the singlet ground state upon deposition. The trifluorosilylphosphinidene was formed through F-migration reactions of FPSiF2 and F3PSi following a two-state mechanism under irradiation with visible light (λ = 470 nm) and full arc light (λ > 220 nm), respectively. High-level quantum-chemical methods support the identification of F3PSi, FPSiF2, and F3SiP by matrix-isolation IR spectroscopy.

Spectroscopic Study of [Mg, H, N, C, O] Species: Implications for the Astrochemical Magnesium Chemistry.

Magnesium is an abundant metal element in space, and magnesium chemistry has vital importance in the evolution of interstellar medium (ISM) and circumstellar regions, such as the asymptotic giant branch star IRC+10216 where a variety of Mg compounds bearing H, C, N, and O have been detected and proposed as the important components in the gas-phase molecular clouds and solid-state dust grains. Herein, we report the formation and infrared spectroscopic characterization of the Mg-bearing molecules HMg, [Mg, N, C], [Mg, H, N, C], [Mg, N, C, O], and [Mg, H, N, C, O] from the reactions of Mg/Mg+ and the prebiotic isocyanic acid (HNCO) in the solid neon matrix. Based on their thermal diffusion and photochemical behavior, a complex reactivity landscape involving association, decomposition, and isomerization reactions of these Mg-bearing molecules is developed, which can not only help understand the chemical processes of the magnesium (iso)cyanides in astrochemistry but also provide implications on the presence of magnesium (iso)cyanates in the ISM and the chemical model for the dust grain surface reactions. It also provides a new paradigm of the key intermediate nature of the cationic complexes in the formation of neutral interstellar species.

Photoinduced Dual C-F Bond Activation of Hexafluorobenzene Mediated by Boron Atom.

The reaction of laser-ablated boron atoms with hexafluorobenzene (C6 F6 ) was investigated in neon and argon matrices, and the products are identified by matrix isolation infrared spectroscopy and quantum-chemical calculations. The reaction is triggered by a boron atom insertion into one C-F bond of hexafluorobenzene on annealing, forming a fluoropentafluorophenyl boryl radical (A). UV-Vis light irradiation of fluoropentafluorophenyl boryl radical causes generation of a 2-difluoroboryl-tetrafluorophenyl radical (B) via a second C-F bond activation. A perfluoroborepinyl radical (C) is also observed upon deposition and under UV-Vis light irradiation. This finding reveals the new example of a dual C-F bond activation of hexafluorobenzene mediated by a nonmetal and provides a possible route for synthesis of new perfluorinated organo-boron compounds.

Kinetics of tautomerisation of thiouracils and cognate species at low temperatures: theory versus experiment.

Hydrogen-atom tunnelling is an important component in some chemical reactions particularly at low temperatures ≤300 K. Recent experiments by Rostkowska et al. [H. Rostkowska, L. Lapinski and M. J. Nowak, Intramolecular Hydrom-Atom Tunnelling in Matrix-Isolated Heterocyclic Compounds: 2-Thiouracil and Its Analogues, Phys. Chem. Chem. Phys., 2024, 26, 23944-23950.] showed that higher energy monomeric conformers of thiouracil and cognate species (thiols) prepared on neon and argon matrices at 3.5 K spontaneously reverted to the lower energy conformer (thiones) presumably by hydrogen-atom quantum mechanical tunnelling. We have shown that these observations can be rationalised by carrying out chemical kinetic calculations employing canonical variational transition state theory with tunnelling effects on these systems in the gas-phase. We show that tunnelling is totally dominant in these systems from 300 K down and discount the possibility of adventitious water contaminating the experimental observations.

Beryllium Dimer Reactions with Acetonitrile: Formation of Strong Be-Be Bonds.

Laser ablated Be atoms have been reacted with acetonitrile molecules in 4 K solid neon matrix. The diberyllium products BeBeNCCH3 and CNBeBeCH3 have been identified by D and 13C isotopic substitutions and quantum chemical calculations. The stabilization of the diberyllium species is rationalized from the formation of the real Be-Be single bonds with bond distances as 2.077 and 2.058 Å and binding energies as -27.1 and -77.2 kcal/mol calculated at CCSD (T)/aug-cc-pVTZ level of theory for BeBeNCCH3 and CNBeBeCH3, respectively. EDA-NOCV analysis described the interaction between Be2 and NC···CH3 fragments as Lewis "acid-base" interactions. In the complexes, the Be2 moiety carries positive charges which transfer from antibonding orbital of Be2 to the bonding fragments significantly strengthen the Be-Be bonds that are corroborated by AIM, LOL and NBO analyses. In addition, mono beryllium products BeNCCH3, CNBeCH3, HBeCH2CN and HBeNCCH2 have also been observed in our experiments.

Influence of heteroatoms and substituents on structural and spectroscopic parameters of saturated six-member ring heterocycles: experimental and theoretical study of 1-methyl-1-germacyclohexane

The conformational analysis of newly synthesized compound, 1-methyl-1-germacyclohexane, is performed by means of a combined vibrational spectroscopy and theoretical methods. The liquid 1-methyl-1-germacyclohexane at room temperature is investigated using conventional ATR-FTIR, FT-IR (gas phase) and Raman methods. FT-IR spectra of the isolated in low-temperature neon and nitrogen matrices are registered. The further detailed vibrational conformational analysis is performed utilizing density functional theory and perturbation theory based methods. All possible 12 canonical ring conformations considering axial/equatorial CH3 group position are analyzed by utilizing DFT/B3LYP, DFT/M06-2X and MP2 at aug-cc-pVTZ theory level.The most stable conformer with the global energy minimum structure in the chair axial conformation is investigated in detail. Analysis of the potential energy surface reveals transition states (TS) and energy barriers. The conformational path is found to be as follows: chair (1C4)→ envelope/half-chair (TS)→ skew-boat (1S3 - C1 symmetry)→ boat (TS)→ skew-boat (1S5 - C2 symmetry). The energy barrier for 1C4 (chair) to 1S3 (skew-boat) conversion is 4.8 kcal/mol while for the reverse process equals to 0.5 kcal/mol.A similar conformational analysis is performed for different configurations of germacyclohexane, silacyclohexane and cyclohexane with mono- and disubstituents: CH2Cl, CH3, Cl and F. Such approach enables investigation of influence of the heteroatoms and substituents of various size and type on the structural parameters and conformational diversity.

Photoelectron Spectroscopy Confirms the Gas-Phase Stability of the C3O2- Anion.

The carbon suboxide anion with an asymmetric zigzag structure, C3O2-, which was recently characterized in a solid neon matrix, has not been observed in the gas phase. Here, we have experimentally generated C3O2- in a supersonic plasma jet expansion and studied it by negative ion photoelectron spectroscopy. A spectral analysis based on the calculated Franck-Condon factors, in combination with quantum chemical calculations, has for the first time yielded a determination of the electron affinity of the neutral carbon suboxide, EA = +0.48(8) eV. Molecular orbital (MO) analysis indicates that, upon linear-to-zigzag geometric change, additional σ-π MO mixing significantly reduces the energy of the singly occupied MO of C3O2- and thus stabilizes the negative ion in the gas phase. This work provides a benchmark understanding of the gas-phase stability of the C3O2- anion.

Calculation of the local environment of a barium monofluoride molecule in a neon matrix

ABSTRACT The local environment of a barium monofluoride (BaF) molecule embedded in a neon matrix is studied theoretically. The energy of the BaF-Ne triatomic system is calculated with a scalar relativistic Hamiltonian, using coupled-cluster theory at the CCSD(T) level for 1625 positions of the Ne atom relative to the BaF molecule. The calculations are repeated with increasing basis sets (from double to quintuple zeta), and are extrapolated to estimate the complete-basis-set limit. Using the potential obtained from these calculations, it is determined that substituting a BaF molecule for ten Ne atoms is favoured compared to substitutions for other numbers of Ne atoms. The equilibrium position and orientation of the BaF molecule and the displacement of its nearby Ne neighbours are determined. The potential barriers that prevent the BaF molecule from migrating and rotating are calculated. These barriers are essential for the EDM 3 collaboration, which is using BaF molecules embedded in a noble-gas solid to perform a precision measurement of the electron electric dipole moment.

Infrared Spectroscopic and Theoretical Investigations of Group 13 Oxyfluorides OMF2 and OMF (M=B, Al, Ga, In).

Group 13 oxyfluorides OMF2 were produced by the reactions of laser-ablated group 13 atoms M (M=B, Al, Ga and In) with OF2 and isolated in excess neon or argon matrices at 5 K. These molecules were characterized by matrix-isolation infrared spectroscopy and isotopic substitution experiments in conjunction with quantum-chemical calculations. The calculations indicate that the OMF2 molecules have a 2 B2 ground state with C2v symmetry. The computed molecular orbitals and spin densities show that the unpaired electron is mainly located at the terminal oxygen atom. Oxo monofluorides OMF were only observed in solid argon matrices and exhibit a linear structure in the singlet ground state. The M-O bonding in the OMF molecules can be rationalized as highly polar multiple bonds based on the calculated bond lengths and natural resonance theory (NRT) analyses. In particular, the molecular orbitals of OBF exhibit the character of a triple bond B-O resulting from two degenerate electron-sharing π bonds and an O→B dative σ bond formed by the oxygen 2p lone pair which donates electron density to the boron empty 2p orbital.

Vibrationally resolved electronic spectroscopy of rhodamine B cation at less than 5 K: combining gas phase absorption and matrix isolation fluorescence spectroscopy

Helium tagging photodissociation action spectroscopy in the gas phase together with laser-induced fluorescence (LIF) spectroscopy in neon matrix has been used to probe the photophysics of electrosprayed rhodamine B cation cooled to < 5 K and studied in two different minimally perturbing environments ([RhB•He]+ as well as [RhB]+ in solid neon). Helium tagging experiments were performed using a newly developed apparatus He-TAG. LIF measurements were carried out using an improved matrix-isolation spectroscopy machine Depo-II. The resulting, partially vibrationally resolved electronic spectra of the S0→S1, resp. S1→S0 transition provide benchmarks for gauging the theoretical description of this prototypical organic dye. As a first approach, we have compared our spectra to TD-DFT-based predictions of vibronic structure at the Franck-Condon (FC) and Franck-Condon Herzberg-Teller (FCHT) levels. Depletion action and fluorescence spectroscopy of rhodamine B cation at < 5 K

Structure of crystalline water ice formed through neon matrix sublimation under cryogenic and vacuum conditions.

Ice I has three forms depending on the stacking arrangements of its layers: hexagonal ice Ih, cubic ice Ic, and stacking disordered ice Isd. Below ∼60K, amorphous water becomes metastable, and the formation of any form of ice I is often implicitly precluded. Using a newly developed low-temperature reflection high-energy electron diffraction (RHEED) technique, we show that crystalline ice with cubic stacking sequences (i.e., ice Ic) formed through Ne sublimation from a solid H2O/Ne (1:1000 ratio) matrix at 13K. The extent of stacking disorder (disordered cubic and hexagonal stacking sequences) in the ice formed by Ne matrix sublimation is smaller than that in vapor-deposited ice Isd prepared at 143K and below the limit of detection of low-temperature RHEED. Dependence of the resulting ice structures on the thickness of the H2O/Ne matrix shows that amorphous water first forms in the early stages of Ne sublimation, and the cubic stacking sequence subsequently takes place. As the cubic ice Ic formed here at a much lower temperature (13K) than previously observed (typically above 78K), Ne matrix sublimation represents a novel route to the formation of cubic ice Ic under low-temperature and low-pressure conditions.

Phosphorus-Boron Multiple Bonding in the π Radical HBP.

The HBP radical was generated via the reaction of laser ablated boron atom with PH3 in a solid neon matrix, which is identified via IR spectroscopy with isotopic substitutions and quantum chemical calculations. The results show that HBP has a 2 Π electronic ground state with a short B-P bond. Bonding analysis indicates that besides an electron-sharing σ bond, there are two degenerate π bonding orbitals that are occupied by three electrons, resulting in a bond order of two and half between P and B. This is in sharp contrast to the bonding properties of the isovalent HNB, which was characterized to be a N≡B triply bonded σ radical with the unpaired electron locating on the B atom.

Nitrogen Trifluoride Complexes of Group 10 Transition Metals M(NF3) (M = Pd, Pt).

The group 10 transition metal atoms Pd and Pt react with nitrogen trifluoride (NF3) forming N-coordination M(NF3) complexes in solid neon and argon matrices. The M(NF3) complexes isomerize to more stable fluoronitrenoid FNMF2 isomers via fluorine migration upon blue LED (λ = 470 nm) light irradiation. These products are characterized on the basis of infrared absorption spectroscopy with isotopic substitutions and theoretical frequency calculations. The analysis of the electronic structure of nitrogen trifluoride complexes indicates that the bonding between metal and nitrogen trifluoride can be described as σ donation from the HOMO of nitrogen trifluoride to the empty metal dz2 orbital and π back-donation from the metal dxz/yz orbitals to the LUMO of nitrogen trifluoride, the latter of which stabilized the metal ligand bond and destabilized the ligand N-F bond. In FNMF2, the FN ligand doubly bonded to the metal and bear imido character.