Ta+ and Nb+ + CO2: intersystem crossing in ion-molecule reactions.

The reactions of Ta+ and Nb+ with CO2 proceed only by a highly efficient oxygen atom transfer reaction to the respective oxide at room temperature in the gas phase. Although the product spin states are not determined, thermochemistry dictates that they must be different from ground state quintet Ta+ and Nb+, implying that intersystem crossing (ISC) has occurred. Recent reactive scattering experiments found dominant indirect dynamics for the reaction with Ta+ hinting at a bottleneck along the reaction path. The question on the nature of the bottleneck, whether it involves a crossing point or a transition state, could not be finally answered because theory located both close to each other. Here, we aim at shedding further light onto the impact of intersystem crossing on the reaction dynamics and ultimately the reactivity of transition metal ion reactions in the gas phase. We employ a combination of thermal kinetics for Ta+ and Nb+ with CO2 using a selected-ion flow tube (SIFT) apparatus and differential scattering cross sections for Nb+ + CO2 from crossed-beam velocity map imaging. The reaction with niobium again shows dominant indirect dynamics and in general very similar dynamics compared to Ta+ + CO2. At thermal energies, both reactions show sub-collisional rate constants with small negative temperature dependencies. Experiments are complemented by high level quantum chemical calculations of the minimum energy pathway. Statistical modelling well-reproduces the experimental thermal rate constants, and suggests that the Nb+ reaction is rate-limited by the intersystem crossing at thermal energies.

Temperature-Dependent Kinetics for the Reactions of Fen- (n = 2-17) and FexNiy- (x + y = 3-9) with O2: Comparison of Pure and Mixed Metal Clusters with Relevance to Meteor Radio Afterglows and Surface Oxidation.

Rate constants and product branching fractions were measured from 300-600 K for Fen- + O2 (n = 2-17) and for 300-500 K for FexNiy- + O2 (x + y = 3-9) using a selected-ion flow tube (SIFT) apparatus. Rate constants for 46 species are reported. All rate constants increased with increasing temperature, and several were in excess of the Langevin-Gioumousis-Stevenson (LGS) capture rate at elevated temperatures. As with previously studied transition metal anion oxidation reactions, the collision limit is treated as the sum of the LGS limit along with a hard-sphere contribution, allowing for determination of activation energies. These values are compared to each other along with previous results for Nin-. Measured rate constants for all three series (Fen-, Nin-, and FexNy-) vary over a relatively narrow range (1-5 × 10-10 cm3 s-1 at 300 K) being at least 15% of the collision rate constant. All reaction rate constants increase with temperature, described by small activation energies of 0.5-4 kJ mol-1. The data are consistent with an anticorrelation between the electron binding energy and rate constant, previously noted in other systems. The Fen- reaction produces a larger population of higher energy electrons than do the Nin- reactions, with FexNiy- producing an intermediate amount. The results suggest that the overall rate constant is limited by a small energetic barrier located at a large internuclear distance where electrostatic forces dominate, causing the potentials to be similar across systems, while the product formation is determined by the shorter-range, valence portion of the potential, which varies widely between systems.

Kinetics of O3 with Ca+ and Its Higher Oxides CaOn+ (n = 1-3) and Updates to a Model of Meteoric Calcium in the Mesosphere and Lower Thermosphere.

The room-temperature rate constants and product branching fractions of CaOn+ (n = 0-3) + O3 are measured using a selected ion flow tube apparatus. Ca+ + O3 produces CaO+ + O2 with k = 9 ± 4 × 10-10 cm3 s-1, within uncertainty equal to the Langevin capture rate constant. This value is significantly larger than several literature values. Most likely, those values were underestimated due to the reformation of Ca+ from the sequential chemistry of higher calcium oxide cations with O3, as explored here. A rate constant of 8 ± 3 × 10-10 cm3 s-1 is recommended. Both CaO+ and CaO2+ react near the capture rate constant with ozone. The CaO+ reaction yields both CaO2+ + O2 (0.80 ± 0.15 branching) and Ca+ + 2O2. Similarly, the CaO2+ reaction yields both CaO3+ + O2 (0.85 ± 0.15 branching) and CaO+ + 2O2. CaO3+ + O3 yield CaO2+ + 2O2 at 2 ± 1 × 10-11 cm3 s-1, about 2% of the capture rate constant. The results are supported using density functional calculations and statistical modeling. In general, CaOn+ + O3 yield CaOn+1+ + O2, the expected oxidation. Some fraction of CaOn+1+ is produced with sufficient internal energy to further dissociate to CaOn-1+ + O2, yielding the same products as the oxidation of O3 by CaOn+. Mesospheric Ca and Ca+ concentrations are modeled as functions of day, latitude, and altitude using the Whole Atmosphere Community Climate Model (WACCM); incorporating the updated rate constants improves agreement with concentrations derived from lidar measurements.

Activation of Methane by Zr+: A Deep-Dive into the Potential Surface via Pressure- and Temperature-Dependent Kinetics with Statistical Modeling.

The kinetics of Zr+ + CH4 are measured using a selected-ion flow tube apparatus over the temperature range 300-600 K and the pressure range 0.25-0.60 Torr. Measured rate constants are small, never exceeding 5% of the Langevin capture value. Both collisionally stabilized ZrCH4+ and bimolecular ZrCH2+ products are observed. A stochastic statistical modeling of the calculated reaction coordinate is used to fit the experimental results. The modeling indicates that an intersystem crossing from the entrance well, necessary for the bimolecular product to be formed, occurs faster than competing isomerization and dissociation processes. That sets an upper limit on the lifetime of the entrance complex to crossing of 10-11 s. The endothermicity of the bimolecular reaction is derived to be 0.09 ± 0.05 eV, in agreement with a literature value. The observed ZrCH4+ association product is determined to be primarily HZrCH3+ not Zr+(CH4), indicating that bond activation has occurred at thermal energies. The energy of HZrCH3+ relative to separated reactants is determined to be -0.80 ± 0.25 eV. Inspection of the statistical modeling results under best-fit conditions reveals reaction dependences on impact parameter, translation energy, internal energy, and angular momentum. Reaction outcomes are heavily affected by angular momentum conservation. Additionally, product energy distributions are predicted.

Gas-Phase Reactivity of Ozone with Lanthanide Ions (Sm+, Nd+) and Their Higher Oxides.

The kinetics of SmOn+ (n = 0-2) and NdOn+ (n = 0-2) with O3 are measured using a selected-ion flow tube. Reaction of Nd+ to yield NdO+ + O2 occurs rapidly, with a rate constant near the capture-controlled limit of ∼8 × 10-10 cm3 s-1. NdO+ reacts at ∼40% of the capture limit to yield NdO2+ with little temperature dependence from 200 to 400 K. NdO2+ likely reacts very slowly (k ∼ 10-13 cm3 s-1) to yield NdO+ + 2O2, does not react to yield NdO3+, and associates slowly (k ∼ 10-12 cm3 s-1) to yield NdO2+(O3)1-3. Reaction of Sm+ also yields SmO+ at near the capture limit at all temperatures, but a significant fraction (∼50%) of the SmO+ is produced in excited states that are long-lived compared to the millisecond time scale of the experiment. These states are evidently resistant to both radiative and collisional relaxation. The excited-state production is likely due to a spin-conservation constraint on the reaction, despite the large spin-orbit coupling typical for lanthanide-containing species. Ground-state SmO+ reacts inefficiently (k = 2 × 10-11 (T/300)-2.5 cm3 s-1) to yield SmO2+ + O2, while the excited-state SmO+* reacts at the capture limit, with branching to yield Sm+ + 2O2 (ΔHr,0K = 148.7 ± 0.4 kJ mol-1 for ground-state SmO+) approximately 60% of the time, the remainder forming SmO2+, which further reacts with O3 to yield SmO+ at about 1% of the collisional value.

Structures and Electron Affinities of Aluminum Hydride Clusters AlnH (n = 3-13).

Low-energy structures and electron affinities (EAs) for aluminum hydride clusters AlnH (n = 3-13) have been calculated using ab initio and density functional calculations. Geometries were optimized at the PBE0/def-2-TZVPP level of theory, which has been shown to match the currently accepted lowest-energy structures for the all-aluminum clusters Aln and their anions. Neutral hydride clusters with n = 4, 7, and 9-12 are predicted to adopt terminal structures with the hydrogen atom bound to only one aluminum atom and with only minor alterations of the aluminum atom arrangement from that of the all-aluminum cluster. Clusters with n = 3 and 13 are predicted to adopt "face-centered" geometries, and the n = 6 cluster is predicted to prefer an isomer with the hydrogen atom bridging two aluminum atoms, also with little or no distortion to the aluminum atom arrangement from the all-aluminum cluster. Addition of a hydrogen atom to clusters with n = 5 and 8 is predicted to distort the aluminum atom arrangement significantly from that of the corresponding all-aluminum cluster. In the anionic clusters, terminal clusters are preferred for all cluster sizes except for n = 6 that prefers a face-centered arrangement. Minor distortions in the aluminum scaffolding for Al11 and Al12 were found, while all other anionic clusters adopt structures with little or no deviation in the aluminum atom arrangement from the corresponding all-aluminum cluster. Raw adiabatic electron affinities were computed using CCSD(T)/aug-cc-pVTZ single-point energies for the anionic and neutral hydride clusters at their respective DFT geometries. Isodesmic electron affinities for the hydride clusters were computed relative to their all-aluminum counterparts and show an even-odd alternation with cluster size. Derived EAs alternate in magnitude between even- and odd-numbered clusters, with the even-numbered clusters having relatively larger EAs.

Effect of Intersystem Crossings on the Kinetics of Thermal Ion-Molecule Reactions: Ti+ + O2, CO2, and N2O.

A selected-ion flow tube apparatus has been used to measure rate constants and product branching fractions of 2Ti+ reacting with O2, CO2, and N2O over the range of 200-600 K. Ti+ + O2 proceeds at near the Langevin capture rate constant of 6-7 × 10-10 cm3 s-1 at all temperatures to yield 4TiO+ + O. Reactions initiated on doublet or quartet surfaces are formally spin-allowed; however, the 50% of reactions initiated on sextet surfaces must undergo an intersystem crossing (ISC). Statistical theory is used to calculate the energy and angular momentum dependences of the specific rate constants for the competing isomerization and dissociation channels. This acts as an internal clock on the lifetime to ISC, setting an upper limit on the order of τISC < 1e-11 s. 2Ti+ + CO2 produces 4TiO+ + CO less efficiently, with a rate constant fit as 5.5 ± 1.3 × 10-11 (T/300)-1.1 ± 0.2 cm3 s-1. The reaction is formally spin-prohibited, and statistical modeling shows that ISC, not a submerged transition state, is rate-limiting, occurring with a lifetime on the order of 10-7 s. Ti+ + N2O proceeds at near the capture rate constant. In this case, both Ti+ON2 and Ti+N2O entrance channel complexes are formed and can interconvert over a barrier. The main product is >90% TiO+ + N2, and the remainder is TiN+ + NO. Both channels need to undergo ISC to form ground-state products but TiO+ can be formed in an excited state exothermically. Therefore, kinetic information is obtained only for the TiN+ channel, where ISC occurs with a lifetime on the order of 10-9 s. Statistical modeling indicates that the dipole-preferred Ti+ON2 complex is formed in ∼80% of collisions, and this value is reproduced using a capture model based on the generic ion-dipole + quadrupole long-range potential.

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.

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.

Role of Spin in the Catalytic Oxidation of CO by N2O Enabled by Co+: New Insights from Temperature-Dependent Kinetics and Statistical Modeling.

The catalytic oxidation of CO by N2O promoted by Co+ was studied as a function of temperature in a variable-ion source temperature-adjustable selected-ion flow tube (VISTA-SIFT). Each step of the cycle, Co+ + N2O and CoO+ + CO was studied individually for unambiguous interpretation of the results. The rate constant of CoO+ + CO is (1.5 ± 0.4) × 10-10 × (T/300 K)-0.7±0.2 cm3 s-1 is in disagreement with a previously reported upper limit of 10-13 cm3 s-1, with the discrepancy likely due to the earlier report having studied the reactions in tandem. The reaction of Co+ + N2O produces CoO+ with a much smaller rate constant of 1.4 ± 0.4 × 10-12 cm3 s-1 at 300 K. The association product, Co(N2O)+, was also produced with a rate constant of 1.6 × 10-28 cm6 s-1. While the rate constant for termolecular association decreased with temperature in accordance with a decreasing time scale for stabilization, the production of CoO+ increased with temperature in a manner that is not well described by simple functional forms. Statistical modeling of calculated reaction coordinates was employed and the experimental data reproduced only by assuming an intersystem crossing to yield ground state CoO+ occurring competitively with the spin-allowed formation of excited state CoO+.

Thermal rate constants for electron attachment to N2O: An example of endothermic attachment.

Rate constants for dissociative electron attachment to N2O yielding O- have been measured as a function of temperature from 400 K to 1000 K. Detailed modeling of kinetics was needed to derive the rate constants at temperatures of 700 K and higher. In the 400 K-600 K range, upper limits are given. The data from 700 K to 1000 K follow the Arrhenius equation behavior described by 2.4 × 10-8 e-0.288 eV/kT cm3 s-1. The activation energy derived from the Arrhenius plot is equal to the endothermicity of the reaction. However, calculations at the CCSD(T)/complete basis set level suggest that the lowest energy crossing between the neutral and anion surfaces lies 0.6 eV above the N2O equilibrium geometry and 0.3 eV above the endothermicity of the dissociative attachment. Kinetic modeling under this assumption is in modest agreement with the experimental data. The data are best explained by attachment occurring below the lowest energy crossing of the neutral and valence anion surfaces via vibrational Feshbach resonances.

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.

Thermal activation of methane by MgO+: temperature dependent kinetics, reactive molecular dynamics simulations and statistical modeling.

The kinetics of MgO+ + CH4 was studied experimentally using the variable ion source, temperature adjustable selected ion flow tube (VISTA-SIFT) apparatus from 300-600 K and computationally by running and analyzing reactive atomistic simulations. Rate coefficients and product branching fractions were determined as a function of temperature. The reaction proceeded with a rate of k = 5.9 ± 1.5 × 10-10(T/300 K)-0.5±0.2 cm3 s-1. MgOH+ was the dominant product at all temperatures, but Mg+, the co-product of oxygen-atom transfer to form methanol, was observed with a product branching fraction of 0.08 ± 0.03(T/300 K)-0.8±0.7. Reactive molecular dynamics simulations using a reactive force field, as well as a neural network trained on thousands of structures yield rate coefficients about one order of magnitude lower. This underestimation of the rates is traced back to the multireference character of the transition state [MgOCH4]+. Statistical modeling of the temperature-dependent kinetics provides further insight into the reactive potential surface. The rate limiting step was found to be consistent with a four-centered activation of the C-H bond, in agreement with previous calculations. The product branching was modeled as a competition between dissociation of an insertion intermediate directly after the rate-limiting transition state, and traversing a transition state corresponding to a methyl migration leading to a Mg-CH3OH+ complex, though only if this transition state is stabilized significantly relative to the dissociated MgOH+ + CH3 product channel. An alternative, non-statistical mechanism is discussed, whereby a post-transition state bifurcation in the potential surface could allow the reaction to proceed directly from the four-centered TS to the Mg-CH3OH+ complex thereby allowing a more robust competition between the product channels.

Methane Adducts of Gold Dimer Cations: Thermochemistry and Structure from Collision-Induced Dissociation and Association Kinetics.

The bond dissociation energies at 0 K (BDE) of Au2+-CH4 and Au2CH4+-CH4 have been determined using two separate experimental methods. Analyses of collision-induced dissociation cross sections for Au2CH4+ + Xe and Au2(CH4)2+ + Xe measured using a guided ion beam tandem mass spectrometer (GIBMS) yield BDEs of 0.71 ± 0.05 and 0.57 ± 0.07 eV, respectively. Statistical modeling of association kinetics of Au2(CH4)0-2+ + CH4 + He measured from 200 to 400 K and at 0.3-0.9 Torr using a selected-ion flow tube (SIFT) apparatus yields slightly higher values of 0.81 ± 0.21 and 0.75 ± 0.25 eV. The SIFT data also place a lower limit on the BDE of Au2C2H8+-CH4 of 0.35 eV, likely an activated isomer, not Au2(CH4)2+-CH4. Particular emphasis is placed on determining the uncertainty in the derivation from association kinetics measurements, including uncertainties in collisional energy transfer, calculated harmonic frequencies, and possible contribution of isomerization of the association complexes. This evaluation indicates that an uncertainty of ±0.2 eV should be expected and that an uncertainty of better than ±0.1 eV is unlikely to be reasonable.

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.

Thermal Kinetics of Aln- + O2 (n = 2-30): Measurable Reactivity of Al13.

Mass-selected aluminum anion clusters, Aln-, were reacted with O2. Rate constants (300 K) for 2 < n < 30 and product branching fractions for 2 < n < 17 are reported. Reactivity is strongly anticorrelated to Aln- electron binding energy (EBE). Al13- reacts more slowly than predicted by EBE but notably is not inert, reacting at a measurable 0.05% efficiency (2.5 ± 1.5 × 10-13 cm3 s-1). Al6- is also an outlier, reacting more slowly than expected after accounting for other factors, suggesting that high symmetry increases stability. Implications of observed Al13- reactivity, contributions of both electronic shell-closing and geometric homogeneity to Aln- resistance to O2 etching, and future directions to more fully unravel the reaction mechanisms are discussed.

Reaction of Mass-Selected, Thermalized V nO m+ Clusters with CCl4.

The kinetics of V nO m+ + CCl4 ( n, m = 2, 5; 3, 6-8; 4, 9-11; 5, 12-13) have been measured under thermal conditions using a selected-ion flow tube equipped with a laser vaporization ion source. All reactions proceed at approximately the capture rate limit, yielding three dominant categories of products: CCl3+ + V nO mCl (i.e., chloride transfer), COCl2 (phosgene) formation, and CO2 formation. Both CO2 and COCl2 are products of CCl4 reaction on a bulk vanadium oxide surface, while chloride (or chlorine) transfer is not observed. The product branching fraction of CCl3+ approaches 100% for small (V2) reactants and generally decreases with increasing cluster size down to <5% for V5O13. The fraction of chloride transfer is correlated to the fraction of terminal oxygen atoms in the V nO m+ reactant. As cluster size increases, phosgene replaces chloride transfer as the dominant product channel. The channel producing CO2 is observed only for highly oxygenated clusters, V3O8+, V4O11+, and V5O13+, and appears to require a superoxide O2 in the reactant structure; the mechanism is likely distinct from that producing CO2 on bulk V2O5. Increasing the temperature of the system from 300 to 500 K increases the observed fraction of CCl3+ at the expense of all other product channels. Likely mechanisms, informed by density functional calculations, are discussed.