Cyclotrimerization of Acetylene under Thermal Conditions: Gas-Phase Kinetics of V+ and Fe+ + C2H2.

The kinetics of successive reactions of acetylene (C2H2) initiated on either vanadium or iron atomic cations have been investigated under thermal conditions using the variable-ion source and temperature-adjustable selected-ion flow tube apparatus. Consistent with the literature results, the reaction of Fe+ + C2H2 primarily yields Fe+(m/z = (C2H2)3); however, analysis via quantum chemical calculations and statistical modeling shows that the mechanism does not form benzene upon the third acetylene addition. The kinetics are more consistent with successive addition of three acetylene molecules, yielding Fe+(C2H2)3, followed by an addition of a fourth acetylene molecule, initiating cyclotrimerization, yielding either Fe+(C2H2) + neutral benzene or Fe+(Bz) + acetylene, where Bz is a benzene ligand. In contrast, the reaction of V+ + C2H2 yields products via successive associations V+(m/z = (C2H2)n) either with or without a bimolecular step involving loss of one H2 and V+C2(m/z = (C2H2)m), where n and m extend at least up to 11 under conditions of 0.32 Torr at 300 K. Stabilized V+(Bz) is not a significant intermediate in the association mechanism. We propose a plausible mechanism for the generation of neutral benzene in this reaction and compare with the Fe+ results. The reaction steps that produce benzene result in turnover of the single-atom catalyst, and the large hydrocarbons produced that remain associated to the catalyst are proposed to be polycyclic aromatic hydrocarbons.

Infrared spectroscopy of the protonated HCl dimer and trimer.

The protonated HCl dimer and trimer complexes were prepared by pulsed discharges in supersonic expansions of helium or argon doped with HCl and hydrogen. The ions were mass selected in a reflectron time-of-flight spectrometer and investigated with photodissociation spectroscopy in the IR and near-IR regions. Anharmonic vibrational frequencies were computed with VPT2 at the MP2/cc-pVTZ level of theory. The Cl-H stretching fundamentals and overtones were measured in addition to stretch-torsion combinations. VPT2 theory at this level confirms the proton-bound structure of the dimer complex and provides a reasonably good description of the anharmonic vibrations in this system. The trimer has a HCl-HClH+-ClH structure in which a central chloronium ion is solvated by two HCl molecules via hydrogen bonding. VPT2 reproduces anharmonic frequencies for this system, including several combinations involving core ion Cl-H stretches, but fails to describe the relative band intensities.

Electronic structure of NdO via slow photoelectron velocity-map imaging spectroscopy of NdO--.

Electronically excited NdO is a possible product of the chemistry associated with the release of Nd into the ionosphere, and emission from these states may contribute to the observations following such experiments. To better characterize the energetics and spectroscopy of NdO, we report a combined experimental and theoretical study using slow photoelectron velocity-map imaging spectroscopy of cryogenically cooled NdO- anions (cryo-SEVI) supplemented by wave function-based quantum-chemical calculations. Using cryo-SEVI, we measure the electron affinity of NdO to be 1.0091(7) eV and resolve numerous transitions to low-lying electronic and vibrational states of NdO that are assigned with the aid of the electronic structure calculations. Additionally, temperature-dependent data suggest contributions from the (2)4.5 state of NdO- residing 2350 cm-1 above the ground anion state. Photodetachment to higher-lying excited states of NdO is also reported, which may help to clarify observations from prior release experiments.

Gas-Phase Anionic Metal Clusters are Model Systems for Surface Oxidation: Kinetics of the Reactions of Mn- with O2 (M = V, Cr, Co, Ni; n = 1-15).

The reactions of anionic metal clusters Mn- with O2 (M = V (n = 1-15), Cr (n = 1-15), Co (n = 1-12), and Ni (n = 1-14)) are investigated from 300 to 600 K using a selected-ion flow tube. All rate constants show a positive temperature dependence, well described by an Arrhenius equation. Rate constants exceed (or are extrapolated to exceed at higher temperatures) the Langevin-Gioumousis-Stevenson capture rate constant. Application of a capture model accounting for the finite size of the clusters reproduces the size-dependent trends in reactivity. The assumption that reactivity is further controlled by an energetic barrier early in the reaction coordinate is consistent with the experimental observations. An observed correlation of the derived barrier heights on the electron binding energy of Mn- suggests the barrier may be formed at an avoided crossing between electronic states correlating to Mn- + O2 and Mn + O2- reactants, analogous to that previously proposed for Aln- + O2 systems. The mechanism is analogous to that for reactions of O2 with neutral metal surfaces, indicating that gas-phase reactions of anionic metal clusters can be an appropriate model systems for surface oxidation.

Infrared spectroscopy of H+(CO)2 in the gas phase and in para-hydrogen matrices.

The H+(CO)2 and D+(CO)2 molecular ions were investigated by infrared spectroscopy in the gas phase and in para-hydrogen matrices. In the gas phase, ions were generated in a supersonic molecular beam by a pulsed electrical discharge. After extraction into a time-of-flight mass spectrometer, the ions were mass selected and probed by infrared laser photodissociation spectroscopy in the 700 cm-1-3500 cm-1 region. Spectra were measured using either argon or neon tagging, as well as tagging with an excess CO molecule. In solid para-hydrogen, ions were generated by electron bombardment of a mixture of CO and hydrogen, and absorption spectra were recorded in the 400 cm-1-4000 cm-1 region with a Fourier-transform infrared spectrometer. A comparison of the measured spectra with the predictions of anharmonic theory at the CCSD(T)/ANO1 level suggests that the predominant isomers formed by either argon tagging or para-hydrogen isolation are higher lying (+7.8 kcal mol-1), less symmetric isomers, and not the global minimum proton-bound dimer. Changing the formation environment or tagging strategy produces other non-centrosymmetric structures, but there is no spectroscopic evidence for the centrosymmetric proton-bound dimer. The formation of higher energy isomers may be caused by a kinetic effect, such as the binding of X (=Ar, Ne, or H2) to H+(CO) prior to the formation of X H+(CO)2. Regardless, there is a strong tendency to produce non-centrosymmetric structures in which HCO+ remains an intact core ion.

Barrierless methane-to-methanol conversion: the unique mechanism of AlO.

The kinetics of AlO+ + CH4 are studied from 300-500 K using a selected-ion flow tube. At all temperatures the reaction proceeds near the Langevin-Gioumousis-Stevenson collision rate with two product channels: hydrogen atom abstraction (AlOH+ + CH3, 86 ± 5%) and methanol formation (Al+ + CH3OH, 14 ± 5%). Density functional calculations show the key Al-CH3OH+ intermediate is formed barrierlessly via a mechanism unique to aluminum, avoiding the rate-limiting step common to other MO+. The reaction of Al2O3+ + CH4 follows a similar mechanism to that for AlO+ through to the key intermediate; however, the conversion to methanol occurs only for AlO+ due to favorable energetics attributed to a weaker Al+-CH3OH bond. Importantly, that bond strength may be tuned independent of competing product channels by altering the acidity of the Al with electron-withdrawing or donating groups, indicating a key design criteria to develop a real world Al-atom catalyst.

The Role of Tunneling in the Spectra of H5+ and D5+ up to 7300 cm-1.

The spectra for H5+ and D5+ are extended to cover the region between 4830 and 7300 cm-1. These spectra are obtained using mass-selected photodissociation spectroscopy. To understand the nature of the states that are accessed by the transitions in this and prior studies, we develop a four-dimensional model Hamiltonian. This Hamiltonian is expressed in terms of the two outer H2 stretches, the displacement of the shared proton from the center of mass of these two H2 groups, and the distance between the H2 groups. This choice is motivated by the large oscillator strength associated with the shared proton stretch and the fact that the spectral regions that have been probed correspond to zero, one, and two quanta of excitation in the H2 stretches. This model is analyzed using an adiabatic separation of the H2 stretches from the other two vibrations and includes the non-adiabatic couplings between H2 stretch states with the same total number of quanta of excitation in the H2 stretches. Based on the analysis of the energies and wave functions obtained from this model, we find that when there are one or more quanta of excitation in the H2 stretches the states come in pairs that reflect tunneling doublets. The states accessed by the transitions in the spectrum with the largest intensity are assigned to the members of the doublets with requisite symmetry that are localized on the lowest-energy adiabat for a given level of H2 excitation.

Catalytic Oxidation of CO by N2O Enabled by Al2O2/3+: Temperature Dependent Kinetics and Statistical Modeling.

The reactions of Al2O2+ + N2O and Al2O3+ + CO, forming a catalytic cycle oxidizing CO by N2O, have been investigated from 300 to 600 K in a variable ion source, temperature adjustable, selected-ion flow tube (VISTA-SIFT). Reaction coordinates have been calculated using density functional theory and statistical modeling of those surfaces compared to experimental kinetics data for mechanistic insight. The reaction of Al2O2+ + N2O proceeds at the Su-Chesnavich collisional limit at all temperatures studied, yielding only Al2O3+, with the exception of a small (<5%) amount of association product, Al2O2(N2O)+ at 300 K. The reaction of Al2O3+ with CO produces Al2O2+ with a rate constant of 4.7 ± 1.2 × 10-10 cm3 s-1 at 300 K, decreasing with temperature as T-0.5±0.2. In addition, a significant amount of association product, Al2O3(CO)+, was observed with rate constants for formation ranging from 10-11 to 10-10 cm3 s-1 dependent upon He buffer gas concentration and temperature. Implications of these kinetic measurements with regard to the reactive surface are discussed.

Quantifying the Competition between Intersystem Crossing and Spin-Conserved Pathways in the Thermal Reaction of V+ + N2O.

The kinetics of V+ + N2O and VO+ + N2O are studied using a selected-ion flow tube from 300-600 K at pressures of 0.25-0.70 Torr helium. V+ + N2O yields VO+ (k = 4.9 ± 1.0 (T/300 K)-0.3±0.2 × 10-10 cm3 s-1) in both ground and excited states. The secondary reaction VO+ + N2O → VO2+ + N2 proceeds near the collision rate at >10-10 cm3 s-1, whereas thermalized VO+ + N2O studied as a primary reaction proceeds more than 100× more slowly (k = 4.2 ± 1.0 (T/300 K)-1.4±0.2 × 10-12 cm3 s-1). The results are best explained by contributions of competing pathways in V+ + N2O: a spin crossing to the lower energy 3VO+ in the exit well and a spin-conserved reaction yielding an electronically excited 5VO+. The intersystem crossing occurs in 35 ± 20% and 37 ± 15% of reactive interactions at 300 and 600 K, respectively. Statistical modeling of relevant reaction coordinates supports the lack of a temperature dependence, indicates an intersystem crossing rate constant of 1011 s-1, and yields derived bond and transition state energies.

Redefining the Mechanism of O2 Etching of Aln- Superatoms: An Early Barrier Controls Reactivity, Analogous to Surface Oxidation.

New insights into aluminum anion cluster reactivity with O2 were obtained through temperature-dependent kinetics measurements. Overall reactivity is controlled by a barrier at an avoided crossing where charge is transferred from the cluster to the O2, mechanistically similar to what occurs as O2 approaches a bulk Al surface. Contrary to prior interpretations, spin conservation does not inhibit the reaction of clusters with an odd number of Al atoms. In fact, the only spin constraint in these systems is on the reactivity of even clusters due to repulsive surfaces, not previously recognized. Although the superatom nature of Al13- is manifest in its high electron binding energy (EBE), the mechanism of its reactivity is not special; it reacts with O2 as if it were a small piece of bulk Al. These experiments highlight the sensitivity of Al cluster reactivity with O2 to temperature and EBE, uncovering routes to industrial scale use of aluminum superatom-based materials.

Mid-Infrared Spectroscopy of C7H7+ Isomers in the Gas Phase: Benzylium and Tropylium.

Both prominent C7H7+ isomers, the benzylium and the tropylium cations, were generated in an electrical discharge/supersonic expansion from toluene and cycloheptatriene precursors. Their infrared spectra were measured in the region of 1000-3500 cm-1 using photodissociation of the respective argon- and nitrogen-tagged complexes with a broadly tunable OPO/OPA laser system. Spectral signatures of both isomers were observed independent of the precursor, albeit in different relative intensities. The spectra were assigned based on scaled harmonic B3LYP-D3/cc-pVTZ frequency computations and comparisons to previous experimental studies. Consistent with its high symmetry, only two bands were observed for the (nitrogen-tagged) tropylium ion at 3036 and 1477 cm-1, corresponding to C-H stretching and C-C-H deformation/C═C stretching vibrations, respectively. Furthermore, the C-H stretching region of the benzylium ion is reported for the first time.

Communication: Infrared photodissociation spectroscopy of the H6+ cation in the gas phase.

The H6+ cation was generated in a pulsed-discharge supersonic expansion of hydrogen and mass-selected in a time-of-flight spectrometer. Its vibrational spectrum was measured in the region of 2050-4550 cm-1 using infrared photodissociation with a tunable OPO/OPA laser system. The H6+ photodissociates, producing H5+, H4+, and H3+ fragments; each of these fragment channels has a different spectrum. Computational studies identify two low-lying isomers described in previous work, whose energies were evaluated at the CCSD(T)/cc-pVTZ//MP2/cc-pVTZ level of theory. A D2d species having an H2+ cation bridging between two perpendicular H2 molecules is the global minimum structure. A Cs structure with an H3+ core ion bound to both H2 and an H atom lies 4.0 kcal mol-1 higher in energy. Anharmonic vibrational spectra were computed for each of these isomers with second-order vibrational perturbation theory (VPT2) in combination with density functional theory at the B2PLYP/cc-pVTZ level. The comparison between experimental and predicted spectra confirms the presence of both the D2d and Cs structures and explains the spectra in different fragmentation channels. Although we find reasonable agreement between the experiment and the spectra predicted by VPT2 computations, a more sophisticated computational approach is needed to better understand this complex system.

Temperature and Isotope Dependent Kinetics of Nickel-Catalyzed Oxidation of Methane by Ozone.

The temperature dependent kinetics of Ni+ + O3 and of NiO+ + CH4/CD4 are measured from 300 to 600 K using a selected-ion flow tube apparatus. Together, these reactions comprise a catalytic cycle converting CH4 to CH3OH. The reaction of Ni+ + O3 proceeds at the collisional limit, faster than previously reported at 300 K. The NiO+ product reacts further with O3, also at the collisional limit, yielding both higher oxides (up to NiO5+ is observed) as well as undergoing an apparent reduction back to Ni+. This apparent reduction channel is due to the oxidation channel yielding NiO2+* with sufficient energy to dissociate. 4NiO+ + CH4 (CD4) (whereas 4NiO+ refers to the quartet state of NiO+) proceeds with a rate constant of (2.6 ± 0.4) × 10-10 cm3 s-1 [(1.8 ± 0.5) × 10-10 cm3 s-1] at 300 K and a temperature dependence of ∼ T-0.7±0.3 (∼ T-1.1±0.4), producing only the 2Ni+ + 1CH3OH channel up to 600 K. Statistical modeling of the reaction based on calculated stationary points along the reaction coordinate reproduces the experimental rate constant as a function of temperature but underpredicts the kinetic isotope shift. The modeling was found to better represent the data when the crossing from quartet to doublet surface was incomplete, suggesting a possible kinetic effect in crossing from quartet to doublet surfaces. Additionally, the modeling predicts a competing 3NiOH+ + 2CH3 channel to become increasingly important at higher temperatures.

Spectroscopy of Proton Coordination with Ethylenediamine.

Protonated ethylenediamine monomer, dimer, and trimer were produced in the gas phase by an electrical discharge/supersonic expansion of argon seeded with ethylenediamine (C2H8N2, en) vapor. Infrared spectra of these ions were measured in the region from 1000 to 4000 cm-1 using laser photodissociation and argon tagging. Computations at the CBS-QB3 level were performed to explore possible isomers and understand the infrared spectra. The protonated monomer exhibits a gauche conformation and an intramolecular hydrogen bond. Its parallel shared proton vibration occurs as a broad band around 2785 cm-1, despite the formally equivalent proton affinities of the two amino groups involved, which usually leads to low frequency bands. The barrier to intramolecular proton transfer is 2.2 kcal mol-1 and does not vanish upon addition of the zero-point energy, unlike the related protonated ammonia dimer. The structure of the dimer is formed by chelation of the monomer's NH3+ group, thereby localizing the excess proton and increasing the frequency of the intramolecular shared proton vibration to 3157 cm-1. Other highly fluxional dimer structures with facile intermolecular proton transfer and concomitant structural reorganization were computed to lie within 2 kcal mol-1 of the experimentally observed structure. The spectrum of the trimer is rather diffuse, and a clear assignment is not possible. However, an isomer with an intramolecular proton transfer like that of the monomer is most consistent with the experimental spectrum.

An Argon-Oxygen Covalent Bond in the ArOH+ Molecular Ion.

The OH+ cation is a well-known diatomic for which the triplet (3 Σ- ) ground state is 50.5 kcal mol-1 more stable than its corresponding singlet (1 Δ) excited state. However, the singlet forms a strong donor-acceptor bond to argon with a bond energy of 66.4 kcal mol-1 at the CCSDT(Q)/CBS level, making the singlet ArOH+ cation 3.9 kcal mol-1 more stable than the lowest energy triplet complex. Both singlet and triplet isomers of this molecular ion were prepared in a cold molecular beam using different ion sources. Infrared photodissociation spectroscopy in combination with messenger atom tagging shows that the two spin isomers exhibit completely different spectral signatures. The ground state of ArOH+ is the predicted singlet with a covalent Ar-O bond.

Cryo IR Spectroscopy of N2 and H2 on Ru8+: The Effect of N2 on the H-Migration.

We present the cryo IR-PD spectra of the coadsorbed [Ru8(H2)1(N2)4]+ and [Ru8(N2)4(H2)1]+ species differing in the adsorption sequence of H2 and N2, which we record via application of tandem cryo ion trapping. We observe strong evidence for dissociative H2 adsorption, and the spectra reveal differences in the Ru-H stretching region, which we assign to distal and proximal hydrogen atom locations on the Ru8+ cluster, their migration likely hindered by preloaded nitrogen molecules and unaffected by subsequent N2 adsorption.

Infrared Spectroscopy of the Astrochemically Relevant Protonated Formaldehyde Dimer.

The protonated formaldehyde dimer (H2CO)2H+ was generated in an electrical discharge and supersonic expansion of argon saturated with formalin solution vapor. Its infrared spectrum was measured in the region from 900 to 4000 cm-1 employing infrared laser photodissociation and messenger atom tagging. Comparison of the experiment to quantum chemical computations at the CCSD(T)/cc-pVQZ//MP2/cc-pVTZ level reveals that the experimentally observed structure is the head-to-tail dimer and not the more stable proton-bound dimer. This is consistent with the usually observed C-O bond formation upon formaldehyde oligomerization under acidic conditions in solution and resembles the structure of the neutral (H2CO)2 dimer in the gas phase. There is no evidence for the formation of other isomers, most notably protonated glycolaldehyde, that could result from covalent bond formation. These findings may be relevant to a proposed carbohydrate formation mechanism in the interstellar medium starting from protonated formaldehyde dimer.

Near-infrared spectroscopy and anharmonic theory of the H2O+Ar1,2 cation complexes.

Weakly bound complexes of the water radical cation with argon (H2O+Arn, n = 1,2) were generated by an electrical discharge/supersonic expansion and probed with mid- and near-infrared photodissociation spectroscopy in the 2050-4550 and 4850-7350 cm-1 regions. To elucidate these spectra, these complexes were studied computationally at the CCSD(T) level including anharmonicity with the VPT2 method. The comparison between experiment and predicted spectra demonstrates that the VPT2 method is adequate to capture most of the vibrational band positions and their intensities. In addition to the fundamentals, overtones of the symmetric and the asymmetric water stretches and their combination were detected. Additional bands were assigned to combinations of the overtone of the bound O-H stretch with multiple excitation levels of the intermolecular Ar-H stretch. H2O+Ar2 could not be dissociated in the higher frequency region (4850-7350 cm-1).

Discrepancy Between Experimental and Theoretical Predictions of the Adiabaticity of Ti+ +CH3 OH.

The reaction between Ti+ and methanol (CH3 OH) is a model system for competition between activation of C-O, C-H, and O-H bonds and of the role of excited electronic pathways in catalytic processes. Herein, we use experimental kinetics, quantum chemical calculations, and statistical modeling to identify the critical features of the reaction's potential energy surface. Experimental kinetics data between 300 and 600 K shows the reaction largely proceeds through C-O bond activation, yielding TiOH+ and TiO+ . Products of the O-H activation pathway, TiOCH2+ and TiOCH3+ are minor, whereas C-H bond activation is not observed at thermal energies. Statistical modeling well-reproduces the experimental results and offers insight into the reaction mechanism. Notably, efficient spin-crossing along the C-O activation pathway is required to produce the observed product distribution, in contrast to a previous estimate of inefficient crossing based on calculation of a small spin-orbit coupling constant. This discrepancy highlights a potential limitation of simple models within the Landau-Zener framework, which are commonly used to calculate surface-crossing probabilities in reactive systems.