Matrix Isolation Experiments Research Articles

Experimental and theoretical investigation of hydrogen bonded complexes between glycolic acid and water

Theoretical MP2 and B3LYPD3 calculations, as well as experimental matrix isolation infrared spectroscopy studies, were used to investigate the 1:1 complexes formed between glycolic acid and water. Out of five computationally predicted forms of GA⋯H2O complex the most stable one was detected experimentally in solid argon. This structure is characterized by two intermolecular OH⋯O hydrogen bonds depicting a six-member ring in which water acts both as a proton acceptor and as a proton donor. Two other structures with the alcoholic OH group acting as a proton donor are also tentatively suggested to be present in solid argon.

Aggregation of N-Heteropolycyclic Aromatic Molecules: The Acridine Dimer and Trimer.

Polycyclic aromatic hydrocarbons and their nitrogen-substituted analogues are of great interest for various applications in organic electronics. The performance of such devices is determined not only by the properties of the single molecules, but also by the structure of their aggregates, which often form via self-aggregation. Gaining insight into such aggregation processes is a challenging task, but crucial for a fine-tuning of the materials properties. In this work, an efficient approach for the generation and characterisation of aggregates is described, based on matrix-isolation experiments and quantum-chemical calculations. This approach is exemplified for aggregation of acridine. The acridine dimer and trimer are thoroughly analysed on the basis of experimental and calculated UV and IR absorption spectra, which agree well with each other. Thereby a novel structure of the acridine dimer is found, which disagrees with a previously reported one. The calculations also show the changes from excitonic coupling towards orbital interactions between two molecules with decreasing distance to each other. In addition, a structure of the trimer is determined. Finally, an outlook is given on how even higher aggregates can be made accessible through experiment.

Stability of monomeric indigo in the electronic ground state: An experimental matrix isolation infrared and theoretical study

Monomers of indigo were investigated using experimental (matrix-isolation) and theoretical methods. For the first time, the infrared spectrum of indigo molecules isolated in low-temperature Ar matrices was recorded and subjected to a detailed theoretical analysis. An excellent agreement between the experimental spectrum of indigo monomers and the spectrum theoretically predicted for the highly-symmetric (C2h) most stable dioxo form of the compound allowed a very reliable assignment of the observed infrared absorption bands. Matrix-isolated monomers of indigo were exposed to UV–vis radiation of different wavelengths. The conducted experiments demonstrated that molecules of indigo do not undergo any structural changes, even under irradiation with short-wavelength UV (λ > 200 nm) light. Theoretical calculations concerning the stability of photoproducts that could be potentially generated from indigo were conducted. The calculations carried out for the species generated by hydrogen-atom transfer from N1′ to O atom attached to the opposite ring revealed that both the oxo-hydroxy and dihydroxy tautomers of indigo should be unstable in the ground electronic state. The calculations carried out for the C2H tautomer (which may be generated by a hydrogen atom shift from N1′ to C2 of the opposite ring) led to optimization of the structure that is potentially stable, but very much distorted from planarity.

Heavy-Atom Quantum Tunnelling in Spin Crossovers of Nitrenes.

We simulate two recent matrix‐isolation experiments at cryogenic temperatures, in which a nitrene undergoes spin crossover from its triplet state to a singlet state via quantum tunnelling. We detail the failure of the commonly applied weak‐coupling method (based on a linear approximation of the potentials) in describing these deep‐tunnelling reactions. The more rigorous approach of semiclassical golden‐rule instanton theory in conjunction with double‐hybrid density‐functional theory and multireference perturbation theory does, however, provide rate constants and kinetic isotope effects in good agreement with experiment. In addition, these calculations locate the optimal tunnelling pathways, which provide a molecular picture of the reaction mechanism. The reactions involve substantial heavy‐atom quantum tunnelling of carbon, nitrogen and oxygen atoms, which unexpectedly even continues to play a role at room temperature.

Water Clusters in Interaction with Corannulene in a Rare Gas Matrix: Structures, Stability and IR Spectra

The interaction of polycyclic aromatic hydrocarbons (PAHs) with water is of paramount importance in atmospheric and astrophysical contexts. We report here a combined theoretical and experimental study of corannulene-water interactions in low temperature matrices and of the matrix’s influence on the photoreactivity of corannulene with water. The theoretical study was performed using a mixed density functional based tight binding/force field approach to describe the corannulene-water clusters trapped in an argon matrix, together with Born-Oppenheimer molecular dynamics to determine finite-temperature IR spectra. The results are discussed in the light of experimental matrix isolation FTIR spectroscopic data. We show that in the solid phase, π isomers of (C20H10)(H2O)n, with n = 2 or 3, are energetically favored. These π complexes are characterized by small shifts in corannulene vibrational modes and large shifts in water bands. These π structures, particularly stable in the case of the water trimer where the water cluster is trapped “inside” the corannulene bowl, may account for the difference in photoreactivity of non-planar–compared to planar–PAHs with water. Indeed, planar PAHs such as pyrene and coronene embedded in H2O:Ar matrices form σ isomers and react with water to form alcohols and quinones under low energy UV irradiation, whereas no photoreactivity was observed for corannulene under the same experimental conditions.

Four isomers of In2H2: a careful comparison between theory and experiment

Four constitutional isomers of diindium dihydride have been studied utilising rigorous quantum mechanical methods. Geometries were optimised with the CCSD(T) method using the aug-cc-pwCVTZ basis set and a small-core pseudopotential for the indium atoms. Relative energetics were determined at the CCSD(T)/CBS level of theory, and the higher order δT(Q) contributions are also computed. The monobridged and vinylidene-like isomers lie 10.8 and 13.6 kcal mol above the planar dibridged isomer, respectively. At 0 K, the trans isomer is the least favoured energetically, differing from the dibridged isomer by 16.6 kcal mol. Anharmonic vibrational frequencies were predicted to provide theoretical insight into future experimental studies. Very detailed comparisons are made to matrix isolation experiments from the group of Downs and the group of Andrews. Numerous agreements and disagreements were found.

Boron Tunneling in the "Weak" Bond-Stretch Isomerization of N-B Lewis Adducts.

Some nitrile-boron halide adducts exhibit a double-well potential energy surface with two distinct minima: a "long bond" geometry (LB, a van der Waals interaction mostly based on electrostatics, but including a residual charge transfer component) and a "short bond" structure (SB, a covalent dative bond). This behavior can be considered as a "weak" form of bond stretch isomerism. Our computations reveal that complexes RCN-BX3 (R=CH3 , FCH2 , BrCH2 , and X=Cl, Br) exhibit a fast interconversion from LB to SB geometries even close to the absolute zero thanks to a boron atom tunneling mechanism. The computed half-lives of the meta-stable LB compounds vary between minutes to nanoseconds at cryogenic conditions. Accordingly, we predict that the long bond structures are practically impossible to isolate or characterize, which agrees with previous matrix-isolation experiments.

Anharmonic Vibrational Spectrum and Experimental Matrix Isolation Study of Thioformic Acid Conformers—Potential Candidates for Molecular Cloud and Solar System Observations?

Abstract Thioformic acid (TFA) is the sulfur analog of formic acid, the simplest organic acid. It has three analogs, HCOSH, HCSOH, and HCSSH, each of them having two rotational isomeric (rotameric) forms: trans and cis where the trans form is energetically more stable. In this article, we study computational energetics and anharmonic vibrational spectrum of TFA, including overtone and combination vibrations. We also studied experimental photoisomerization and photodecomposition channels of HCOSH molecules with different wavelengths. We suggest that TFA is a potential sulfur-containing candidate molecule for interstellar and planetary observations and discuss these in light of different radiation environments in space. More generally, we discuss that infrared radiation-driven photoisomerization reactions may be a common phenomenon in such environments and can affect the chemical reaction pathways of organic and other interstellar molecules.

The Peculiar Interaction of Trifluoride Anions with Cryogenic Rare Gas Matrices.

In this contribution, we present theoretical modeling of the interaction between rare gas matrices and a trifluoride guest anion, as well as its quantitative effect on measured vibrational spectra. Using a combination of coupled-cluster electronic structure calculations and a many-body potential expansion coupled with permutation invariant polynomial fitting and anharmonic vibrational spectrum simulations, we shed light on the origin of the trifluoride matrix effects observed experimentally. The theoretical spectra are found to reproduce accurately the measured data while providing deeper insights into the effects of the guest-host interaction. The investigations reveal that neon can only stabilize trifluoride in hexagonal cavities formed by double vacancies, while argon can host the anion in a variety of cavities ranging from zero to two defects in the matrix. The origin of this structural variability can be traced back to the disparate strengths of the host-host interactions in neon and argon. The present work demonstrates the importance of theoretical modeling to complement matrix isolation experiments, which alone do not provide direct information about the structure of the matrices or about the physical origin of their interaction and of their spectroscopic signature.

ICOM formation from radical chemistry: a mechanistic study from cryogenic matrix coupled with IR and EPR spectroscopies

ABSTRACT Interstellar complex organic molecules (iCOMs) have been identified in different interstellar environments including star forming regions as well as cold dense molecular clouds. Laboratory studies show that iCOMs can be formed either in gas phase or in the solid state, on icy grains, from ‘non-energetic’ (atom-addition/abstraction) or energetic (UV-photon, particle bombardments) processes. In this contribution, using a new experimental approach mixing matrix isolation technique, mass spectrometry, and infrared and EPR spectroscopies, we want to investigate the COM formation at 35 K from a complex mixture of ground state radicals trying to draw a general reaction scheme. We photolyse (121 nm) CH3OH diluted in Ar at low temperature (below 15 K) to generate $\mathrm{H^.CO}$, $\mathrm{HO^.CO}$, $\mathrm{^.CH_2OH}$, $\mathrm{CH_3O^.}$, $\mathrm{^.OH}$, and $\mathrm{^.CH_3}$ radicals and ‘free’ H-atoms within the matrix. Radicals have been identified using infrared and EPR spectroscopies. With the disappearance of the Ar matrix (at 35 K), these unstable species are then free to react, forming new species in a solid film. Some recombination products have been detected using infrared spectroscopy and mass spectrometry in the solid film after Ar removal, namely methyl formate (CH3OCHO), glycolaldehyde (HOCH2CHO), ethylene glycol (HOCH2CH2OH), glyoxal (CHOCHO), ethanol (CH3CH2OH), formic acid (HCOOH), dimethyl ether (CH3OCH3), methoxymethanol (CH3OCH2OH), and CH4O2 isomers (methanediol and/or methyl hydroperoxide). The detected molecules are fully consistent with the radicals detected and strongly support the solid state scenario of iCOM formation in interstellar ices based on radical–radical recombination. We then discuss astrophysical implications of the radical pathways on the observed gas phase iCOMs.

Generic accommodations of an atom in the Lennard-Jones fcc and hcp rare-gas solids: A computational study

A comprehensive computational analysis of the stable accommodations of an atom in the Lennard-Jones (LJ) face-centered-cubic (fcc) and hexagonal-closest-packed (hcp) lattices is presented. For a wide range of the guest-host LJ interaction parameters and the number of host atoms removed, $N$, global optimizations are performed to find the minimum energy structures. Stable accommodations are determined using the convex hull of the energy dependence on $N$. The most stable ground accommodations are mapped onto the guest-host LJ parameter space for the hosts representing the rare-gas solids from Ne to Xe. The radial distribution function analysis is used to classify the structures found as originating from the guest placements in the lattice voids or at the node. Ten generic accommodations are identified for each lattice. Comparing to mostly polyhedral structures in fcc, the hcp ones have generally lower symmetry, which should affect the band shapes of atomic absorption spectra. Despite the well-known wrong prediction of higher hcp phase stability in the LJ model, the cases of strong accommodation preferences in one phase or another are identified. Being generic, the obtained results can be useful for a qualitative interpretation of atomic matrix isolation experiments.

Fermi resonance switching in KrH+Rg and XeH+Rg (Rg = Ne, Ar, Kr, and Xe).

Matrix isolation experiments have been successfully employed to extensively study the infrared spectrum of several proton-bound rare gas complexes. Most of these studies have focused on the spectral signature for the H+ stretch (ν3) and its combination bands with the intermolecular stretch coordinate (ν1). However, little attention has been paid to the Fermi resonance interaction between the H+ stretch (ν3) and H+ bend overtone (2ν2) in the asymmetric proton-bound rare gas dimers, RgH+Rg'. In this work, we have investigated this interaction on KrH+Rg and XeH+Rg with Rg = (Ne, Ar, Kr, and Xe). A multilevel potential energy surface (PES) was used to simulate the vibrational structure of these complexes. This PES is a dual-level comprising of second-order Møller-Plesset perturbation theory and coupled-cluster singles doubles with perturbative triples [CCSD(T)] levels of ab initio theories. We found that when both the combination bands (nν1 + ν3) and bend overtone 2ν2 compete to borrow intensity from the ν3 band, the latter wins over the former, which then results in the suppression of the nν1 + ν3 bands. The current simulations offer new assignments for the ArH+Xe and KrH+Xe spectra. Complete basis set (CBS) binding energies for these complexes were also calculated at the CCSD(T)/CBS level.

Matrix isolation in laboratory astrochemistry: state-of-the-art, implications and perspective

Recent progress in observational astronomy and astrophysics has stimulated intensive laboratory studies aimed at elucidating the mechanisms of evolution of molecular matter in interstellar space and various space objects. One of the most intriguing and rapidly developing areas of these studies is the so-called “cold astrochemistry” devoted to the complex processes occurring in astrophysical ices. In this context, the matrix isolation technique (known for decades) is a very useful approach for both interpreting the results of astrophysical observations and verifying possible mechanisms of key astrochemical processes. This review outlines the most important results of recent studies using the matrix isolation technique. In fact, the results of these studies contribute to “cold” astrochemistry in two main aspects: (i) spectroscopy of astrochemically important molecules, ions and radicals stabilized in cryogenic matrices; (ii) experimental modeling of mechanisms of radiation-induced and “in dark” chemical reactions occurring in “cold” space environments (interstellar, cometary and planetary ices). In the first aspect, special attention is paid to new spectroscopic data obtained using various methods (electronic and vibrational absorption spectroscopy, electron paramagnetic resonance spectroscopy). In the second aspect, we consider the chemical effects resulting from both direct excitation of isolated molecules and the transfer of energy initially absorbed by the medium. Special attention has been paid to recent studies of spectroscopic characteristics and radiation-induced evolution of matrix-isolated weak intermolecular complexes, which can be considered “building blocks” for cold synthesis of complex molecules in the absence of diffusion mobility. In addition, we consider the use of matrix isolation for the studies of low-temperature chemical reactions “in dark” involving atoms and highly reactive intermediates, which can occur in cold space environments. In the final part, we briefly discuss the applicability of the results of matrix isolation experiments for interpretation of the mechanisms in molecular ices and highlight the prospects of this field. The review can also be useful for specialists in various aspects of chemistry and chemical physics (radiation chemistry, photochemistry, molecular spectroscopy, low-temperature chemistry).The bibliography includes 379 references.

Theoretical and matrix isolation studies of infrared spectra of the H2CO∙∙∙HF hydrogen-bonded complex

The equilibrium geometry, the binding energy, and harmonic and anharmonic spectral parameters of H2CO and HF monomers and the H2CO∙∙∙HF complex are calculated in the MP2/6-311++G(3df,3pd) approximation with the basis set superposition error taken into account. Anharmonic calculations are carried out using the second-order vibrational perturbation theory. The changes in transition frequencies and intensities of monomeric IR bands upon formation of the 1:1 complex are analyzed. A high intensity value (53 km mol–1) is predicted for the overtone band of the out-of-plane HF libration. The variational method was used to solve anharmonic vibrational problems in 1D–4D subspaces involving the H–F stretch. The influence of anharmonicity on spectral and structural parameters was studied. The variational calculation confirmed the high intensity value for the overtone of the HF librational mode from the perturbative calculation. Matrix-isolation experiments were performed in N2 at T = 8 K to record the absorption spectra of pure H2CO and HF and H2CO/HF mixtures in the IR region. The spectral features related to the H–F, C=O, and C–H stretches and the in-plane HF librational motion were reliably identified. The predictions of our perturbative calculations for isolated compounds, especially for the band shifts upon complexation, are in satisfactory agreement with the experimental matrix-isolation findings. The only exception is the H–F stretching mode in the complex because of the high anharmonicity of HF and strong interaction of free HF molecules with a matrix environment. Of particular interest is the observation of a rather strong band at 1069 cm–1, which is close to 1072 cm–1 predicted for the overtone of HF out-of-plane librational mode.

Quantitative assessment of the absorbed dose in cryodeposited noble-gas films under X-ray irradiation: Simulation vs. experiment

This work was aimed at quantitative determination of the absorbed doses under X-ray irradiation of cryogenic deposited films, particularly related to the matrix isolation experiment. The relative absorbed doses in the layers of solid noble gases of different thickness irradiated with an X-ray tube (46.6 kVp) in the specified cryostat geometry were calculated by Monte-Carlo simulation using a Geant4 code. In order to calibrate the obtained values, the relative absorbed dose in the ferrosulfate dosimeter irradiated in the same geometry was calculated in the same way. The effect of additional Al filter (420 μm) on the photon spectrum and relative absorbed dose in noble gas layers and dosimetric system was simulated. The experimental verification was based on the monitoring of the radiation-induced decay rate of ethane molecules isolated in different solid noble gas matrices (Ar, Kr, and Xe, 1:1000) irradiated in the cryostat at 6 K. It was shown that the simulation reproduces well the experimentally observed effect of the filter on relative absorbed dose rate in both dosimetric system and the layers of different solid noble gases (80–180 μm). Absolute absorbed dose rates were determined as a function of deposited layer thickness in different noble gases. The comparison of the simulation results with a crude estimation based on a single effective energy value is discussed.

Conformational diversity of the THF molecule in N2 matrix by means of FTIR matrix isolation experiment and Car-Parrinello molecular dynamics simulations.

Tetrahydrofuran (THF) is a widely used chemical compound, in particular as a solvent in organic and inorganic synthesis. The THF molecule has also an interesting property, namely, undergoes pseudorotation, similar to the case of the cyclopentane. Low energy difference between the envelope (Cs symmetry) and twisted (C2 symmetry) conformations of the THF molecule leads to the interconversion between the two conformers. We study the influence of the molecular environment (N2) on the Cs-C2 equilibrium of tetrahydrofuran in the THF@N2 system utilizing nitrogen matrix isolation infrared spectroscopy. We observe a different ratio between envelope (Cs) and twisted (C2) conformations with respect to a change of the temperature. FTIR experimental studies are supported by the results of the static density functional theory calculations and Car-Parrinello molecular dynamics simulations. We focus on the dynamics of the pseudorotation process, in particular, the lifetime of the THF conformations and their mutual rearrangements. On the basis of the THF@N2 matrix model, with explicit nitrogen molecules, the anharmonic infrared spectra are generated from the Fourier transformation of the dipole moment autocorrelation function.

Polyhalogen and Polyinterhalogen Anions from Fluorine to Iodine.

This Review deals with the evolving field of polyhalogen chemistry, specifically polyhalogen anions (polyhalides). In addition to a historical outline, current progress in synthetic approaches towards the formation of polyfluorides, polychlorides, polybromides, and polyinterhalides is also illustrated. The structural diversity of polyhalides has substantially increased in the past decade, especially for polychlorides and polybromides, which are commonly characterized by single-crystal X-ray diffraction, Raman spectroscopy, and quantum-chemical calculations. Polyfluorides have been examined by sophisticated state-of-the-art quantum-chemical calculations and investigated spectroscopically in noble gas matrix-isolation experiments under cryogenic conditions at 4 K. The bonding in such polyhalide systems is also discussed. The last Section deals with applications of polyhalides in halogenation reactions and electrochemistry as well as their use as reactive ionic liquids, emphasizing the promising future of polyhalogen chemistry.

Toward Elimination of Discrepancies between Theory and Experiment: Anharmonic Rotational-Vibrational Spectrum of Water in Solid Noble Gas Matrices.

Rotational–vibrational spectroscopy of water in solid noble gas matrices has been studied for many decades. Despite that, discrepancies persist in the literature about the assignment of specific bands. We tackle the involved rotational–vibrational spectrum of the water isotopologues H216O, HD16O, and D216O with an unprecedented combination of experimental high-resolution matrix isolation infrared (MI-IR) spectroscopy and computational anharmonic vibrational spectroscopy by vibrational configuration interaction (VCI) on high-level ab initio potential energy surfaces. With VCI, the average deviation to gas-phase experiments is reduced from >100 to ≈1 cm–1 when compared to harmonic vibrational spectra. Discrepancies between MI-IR and VCI spectra are identified as matrix effects rather than missing anharmonicity in the theoretical approach. Matrix effects are small in Ne (≈1.5 cm–1) and a bit larger in Ar (≈10 cm–1). Controversial assignments in Ne MI-IR spectra are resolved, for example, concerning the ν3 triad in HDO. We identify new transitions, for example, the ν2 101 ← 110 transition in D2O and H2O or the ν3 000 ← 101 transition in D2O, and reassign bands, for example, the band at 3718.9 cm–1 that is newly assigned as the 110 ← 111 transition. The identification and solution of discrepancies for a well-studied benchmark system such as water prove the importance of an iterative and one-hand combination of theory and experiment in the field of high-resolution infrared spectroscopy of single molecules. As the computational costs involved in the VCI approach are reasonably low, such combined experimental/theoretical studies can be extended to molecules larger than triatomics.

Nitrogen Sublimation as a Driver of Chemistry in Pluto-Analog Laboratory Ices: Formation of Carbon Suboxide (C3O2) and Various Salts

A number of planetary bodies, including Triton and Pluto, and a number of Kuiper Belt objects contain nitrogen ices on their surfaces. Nitrogen ices were also used in laboratory experiments as a matrix isolation material before noble gases could be condensed. Planetary bodies with nitrogen ices then may act as giant matrix isolation experiments, trapping reactive species onto the surface and concentrating them. Upon sublimation, these reactive species are much more likely to encounter each other or another molecule to react with. A pilot study was conducted to test the feasibility of testing the chemistry occurring during the sublimation of nitrogen ices. A high vacuum laboratory setup was used to create ices at ∼6 K (±0.5 K). Ices were deposited under microwave radiation to create radicals to simulate what might be present in the tenuous atmospheres of these planetary bodies. The ices consisted of a mixture of 1:1:100 carbon source + H2O + N2, where the carbon source was either CO or CH4. Reagents and products were primarily identified using FTIR and UV–vis transmission spectroscopy. Once the predominantly N2 ice was characterized with the spectroscopic techniques, the N2 was sublimated to create a H2O ice, and then this ice was characterized using the aforementioned techniques. One completely new product was observed, namely, carbon suboxide (C3O2), and a couple products identified in the nitrogen ice formed various salts. Future work could make use of multiple sublimation steps and other astrochemically relevant matrices and introduce more astrophysically relevant sources of radiation like electron beams or UV irradiation.

Ring Expansion of Alkylidenecarbenes Derived from Lactams, Lactones, and Thiolactones into Strained Heterocyclic Alkynes: A Theoretical Study.

Strained cycloalkynes are of considerable interest to theoreticians and experimentalists, and possess much synthetic value as well. Herein, a series of cyclic alkylidenecarbenes—formally obtained by replacing the carbonyl oxygen of four-, five-, and six-membered lactams, lactones, and thiolactones with a divalent carbon—were modeled at the CCSD(T)/cc-pVTZ//B3LYP/6-311+G** and CCSD(T)/cc-pVTZ//CCSD/6-311+G** levels of theory. The singlet carbenes were found to be more stable than the triplets. The strained heterocyclic alkynes formed by ring expansion of these singlet carbenes were also modeled. Interestingly, the C≡C bonds in the five-membered heterocycles, obtained from the rearrangement of β-lactam- and β-lactone-derived alkylidenecarbenes, displayed lengths intermediate between formal double and triple bonds. Furthermore, 2-(1-azacyclobutylidene)carbene was found to be nearly isoenergetic with its ring-expanded isomer, and 1-oxacyclopent-2-yne was notably higher in energy than its precursor carbene. In all other cases, the cycloalkynes were lower in energy than the corresponding carbenes. The transition states for ring-expansion were always lower for the 1,2-carbon shifts than for 1,2-nitrogen or oxygen shifts, but higher than for the 1,2-sulfur shifts. These predictions should be verifiable using carbenes bearing appropriate isotopic labels. Computed vibrational spectra for the carbenes, and their ring-expanded isomers, are presented and could be of value to matrix isolation experiments.