Internal Energy Distribution Research Articles

Generalized Chemistry–Internal Energy Coupling Model Using Prior Recombination Distribution

In this work, the interaction between the internal energy states and the dissociation/recombination process for a diatomic molecule is studied in detail. In particular, the state-specific recombination and dissociation rate constants are derived as a function of internal energy distribution and other molecular parameters. As a special case, applying this result with specific vibrational energy distributions, we obtain the classic Marrone and Treanor models. An information theory approach to obtain the initial recombination distribution for any diatomic molecule is also presented. The general idea is to incorporate the vibrational and the rotational effects in the dissociation and recombination process without a full vibrational-rotational state-specific model. The effect of this rovibrational coupling is to produce an initial recombination distribution that is biased to the high internal energy states. These initial recombination distributions are then thermally averaged to obtain temperature-dependent expressions for different diatomic molecules to characterize the internal energy distribution of recombining molecules.

Measuring the internal energies of species emitted from hypervelocity nanoprojectile impacts on surfaces using recalibrated benzylpyridinium probe ions

We present herein a framework for measuring the internal energy distributions of vibrationally excited molecular ions emitted from hypervelocity nanoprojectile impacts on organic surfaces. The experimental portion of this framework is based on the measurement of lifetime distributions of "thermometer" benzylpyridinium ions dissociated within a time of flight mass spectrometer. The theoretical component comprises re-evaluation of the fragmentation energetics of benzylpyridinium ions at the coupled-cluster singles and doubles with perturbative triples level. Vibrational frequencies for the ground and transition states of select molecules are reported, allowing for a full description of vibrational excitations of these molecules via Rice-Ramsperger-Kassel-Marcus unimolecular fragmentation theory. Ultimately, this approach is used to evaluate the internal energy distributions from the measured lifetime distributions. The average internal energies of benzylpyridinium ions measured from 440 keV Au400(+4) impacts are found to be relatively low (~0.24 eV/atom) when compared with keV atomic bombardment of surfaces (1-2 eV/atom).

Infrared spectroscopic studies on hydrogen-bonded water networks in gas phase clusters

Size-selective infrared (IR) spectroscopy of gas phase water-containing clusters is performed to probe microscopic natures of hydrogen-bonded water networks. Size-selective observation is extended to the size range of a few tens to hundreds of molecules to bridge the gap between simple but unique networks in small-sized water clusters and those in bulk water. IR spectra of two types of large water-containing clusters, phenol-(H2O) n (n < ∼50) and H+(H2O) n (n ⩽ 221), are measured in the OH stretching vibrational region. Clear size dependence of the observed spectra is interpreted in terms of coordination numbers of water molecules, ring sizes of hydrogen bond networks and interior crystallisation of the clusters. Structural features of hydrogen bond networks seen in bulk water are confirmed in these large-sized clusters. For more detailed analyses of spectra of H+(H2O) n , the inert gas ‘tagging’ technique is employed. Tuning of internal energy and isomer distribution of H+(H2O) n is achieved by a choice of inert gas species. An effective approach to spectral isomer separation is proposed on the basis of unexpected inert gas dependence of isomer distribution. Inert gas tagging is also applied to probe hydrogen bond network motifs of large-sized H+(H2O) n in the size range of n = 20−50. A particular success of the tagging is demonstrated on the n = 22 cluster, which has been known as an anti-magic number cluster. An important application of gas phase water clusters is simplification of a complicated phenomenon in liquid water and such model clusters allow us to extract the physical essence of the phenomenon. Radiation chemistry of water (ionisation and following processes) is studied by IR spectroscopy of water cluster radical cations, (H2O) n +. The H3O+–OH ion-radical contact pair formation upon ionisation of water is confirmed in n ⩽ 4. Separation of the ion-radical pair by hydration processes is observed in n ⩾ 5. This result shows the intrinsic instability of the H3O+–OH ion-radical contact pair in water networks, and implies higher mobility of the OH radical due to its release from the charged site.

Laser-induced thermal detachment of hot, large molecular ions under multiphoton-absorption conditions

We observed the delayed electron detachment induced by multiphoton absorption of hot, zinc phthalocyanine negative ions (C${}_{32}$H${}_{16}$N${}_{8}$Zn${}^{\ensuremath{-}}$) stored in an electrostatic ion storage ring. To examine the critical parameters and conditions that characterize the delayed processes, we performed a theoretical model simulation employing inferred values for molecular properties and experimentally controlled values of excitation laser energy and fluence. The thermal detachment rate was estimated by applying the detailed balance theory, and the internal energy distribution of the ions after multiphoton absorption was calculated as a function of the ion temperature immediately before laser irradiation. Our model simulation well reproduces the experimental results, and demonstrates that the experimental configuration determines the range of the observed detachment rate, namely the detectable energy window of the stored ions. The parameter dependence of the estimated ion temperature on the molecular properties was also obtained.

On the Decomposition Mechanisms of New Imidazole-Based Energetic Materials

New imidazole-based energetic molecules (1,4-dinitroimidazole, 2,4-dinitroimidazole, 1-methyl-2,4-dinitroimidazole, and 1-methyl-2,4,5-trinitroimidazole) are studied both experimentally and theoretically. The NO molecule is observed as a main decomposition product from the above nitroimidazole energetic molecules excited at three UV wavelengths (226, 236, and 248 nm). Resolved rotational spectra related to three vibronic bands (0-0), (0-1), and (0-2) of the NO (A (2)Σ(+) ← X (2)Π) electronic transition have been obtained. A unique excitation wavelength independent dissociation channel is characterized for these four nitroimidazole energetic molecules: this pathway generates the NO product with a rotationally cold (10-60 K) and vibrationally hot (1300-1600 K) internal energy distribution. The predicted reaction mechanism for the nitroimidazole energetic molecule decomposition subsequent to electronic excitation is the following: electronically excited nitroimidazole energetic molecules descend to their ground electronic states through a series of conical intersections, dissociate on their ground electronic states subsequent to a nitro-nitrite isomerization, and produce NO molecules. Different from PETN, HMX, and RDX, the thermal dissociation process (ground electronic state decomposition from the Franck-Condon equilibrium point) of multinitroimidazoles is predicted to be a competition between NO(2) elimination and nitro-nitrite isomerization followed by NO elimination for all multinitroimidazoles except 1,4-dinitroimidazole. In this latter instance, N-NO(2) homolysisis becomes the dominant decomposition channel on the ground electronic state, as found for HMX and RDX. Comparison of the stability of nitro-containing energetic materials with R-NO(2) (R = C, N, O) moieties is also discussed. Energetic materials with C-NO(2) are usually more thermally stable and impact/shock insensitive than are other energetic materials with N-NO(2) and O-NO(2) moieties. The imidazole aromatic ring also plays an important role in improving the stability of these energetic materials. Thus, multinitroimidazoles energetic materials can be of significant potential for both civilian and military applications.

Indirect Dynamics in a Highly Exoergic Substitution Reaction

The highly exoergic nucleophilic substitution reaction F(-) + CH3I shows reaction dynamics strikingly different from that of substitution reactions of larger halogen anions. Over a wide range of collision energies, a large fraction of indirect scattering via a long-lived hydrogen-bonded complex is found both in crossed-beam imaging experiments and in direct chemical dynamics simulations. Our measured differential scattering cross sections show large-angle scattering and low product velocities for all collision energies, resulting from efficient transfer of the collision energy to internal energy of the CH3F reaction product. Both findings are in strong contrast to the previously studied substitution reaction of Cl(-) + CH3I [Science 2008, 319, 183-186] at all but the lowest collision energies, a discrepancy that was not captured in a subsequent study at only a low collision energy [J. Phys. Chem. Lett. 2010, 1, 2747-2752]. Our direct chemical dynamics simulations at the DFT/B97-1 level of theory show that the reaction is dominated by three atomic-level mechanisms, an indirect reaction proceeding via an F(-)-HCH2I hydrogen-bonded complex, a direct rebound, and a direct stripping reaction. The indirect mechanism is found to contribute about one-half of the overall substitution reaction rate at both low and high collision energies. This large fraction of indirect scattering at high collision energy is particularly surprising, because the barrier for the F(-)-HCH2I complex to form products is only 0.10 eV. Overall, experiment and simulation agree very favorably in both the scattering angle and the product internal energy distributions.

Fast Radiative Cooling of Anthracene Observed in a Compact Electrostatic Storage Ring

Fast radiative cooling of anthracene was observed in a compact electrostatic storage ring by probing the evolution of the internal energy distribution of a stored (C(14)H(10))(+) molecular ensemble via laser excitation. We have measured the mean radiative decay rate to be about 120 to 250 s(-1) for internal energies in the range from 6.6 to 6.8 eV. Such a high decay rate is 2 orders of magnitude larger than the infrared emission cooling rate expected for vibrational transitions. It is attributed to fluorescence from thermally excited electrons. This fast cooling mechanism may have important implications in astrophysics concerning the lifetime and the critical size of polycyclic aromatic hydrocarbons in interstellar conditions.

Collision cell pressure effect on CID spectra pattern using triple quadrupole instruments: a RRKM modeling

Control of the ion internal energy in mass spectrometry is needed to establish a workable mass spectral library. The purpose of this study is to understand and to compare the pressure effects on the collision-induced dissociation (CID) spectrum pattern recorded using triple quadrupole instruments. The monoprotonated Leucine enkephalin [YGGFL, H(+)] was used as a thermometer molecule to calibrate the electrospray ionization (ESI) and the CID internal energies deposited on the molecular species and the time scale of ion decompositions. The survival yield and the ratio of a(4)/b(4) fragment ions were mainly monitored. The energy uptake for the ESI source geometry used in our study has no impact on the CID spectrum fingerprint. The collision cell pressure for the [YGGFL, H(+)] has a major influence on the SY curves slope and on the experimental time scale. To demonstrate the pressure effect on internal energy distribution, three models (threshold, thermal and collisional) based on RRKM theory were built using the Masskinetics software. As a result, the limit of each model is discussed, and the investigation demonstrates that the thermal model, using truncated Maxwell-Boltzmann internal energy distribution, is well-suited for simulating the experimental data at high pressure widely used in the analytical conditions.

Alkali metal cation–cyclen complexes: Effects of alkali metal cation size on the structure and binding energy

Threshold collision-induced dissociation of alkali metal cation–cyclen complexes, M+(cyclen), with xenon is studied using guided ion beam tandem mass spectrometry techniques. The alkali metal cations examined here include: Na+, K+, Rb+ and Cs+. In all cases, M+ is the only ionic product observed, corresponding to endothermic loss of the intact cyclen ligand. The cross section thresholds are analyzed to extract zero and 298K M+–cyclen bond dissociation energies (BDEs) after properly accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and the lifetimes for dissociation. Density functional theory calculations at the B3LYP/def2-TZVPPD and B3LYP/6-31+G* levels of theory are used to determine the structures of cyclen and the M+(cyclen) complexes. Theoretical BDEs are determined from single point energy calculations at the B3LYP/def2-TZVPPD and MP2(full)/def2-TZVPPD levels of theory using the B3LYP/def2-TZVPPD optimized geometries, and also at the B3LYP/6-311+G(2d,2p) and MP2(full)/6-311+G(2d,2p) levels of theory using the B3LYP/6-31+G*optimized geometries. The agreement between theory and experiment is reasonably good for all levels of theory examined, but is best for the calculations performed at the B3LYP/def2-TZVPPD level of theory. The M+–cyclen BDEs decrease as the size of the alkali metal cation increases, consistent with the electrostatic nature of the binding in these complexes. The M+(cyclen) structures and BDEs are compared to those previously reported for the analogous M+(12-crown-4) complexes to examine the effects of the donor atom (N versus O) on the structures and strength of binding.

Structural and Energetic Effects in the Molecular Recognition of Acetylated Amino Acids by 18-Crown-6

Absolute 18-crown-6 (18C6) binding affinities of four protonated acetylated amino acids (AcAAs) are determined using guided ion beam tandem mass spectrometry techniques. The AcAAs examined in this work include: N-terminal acetylated lysine (N(α)-AcLys), histidine (N(α)-AcHis), and arginine (N(α)-AcArg) as well as side chain acetylated lysine (N(ε)-AcLys). The kinetic-energy-dependent cross sections for collision-induced dissociation (CID) of the (AcAA)H(+)(18C6) complexes are analyzed using an empirical threshold law to extract absolute 0 and 298 K (AcAA)H(+)-18C6 bond dissociation energies (BDEs) after accounting for the effects of multiple collisions, kinetic and internal energy distributions of the reactants, and unimolecular dissociation lifetimes. Theoretical electronic structure calculations are performed to determine stable geometries and energetics for neutral and protonated 18C6 and the AcAAs as well as the proton bound complexes of these species, (AcAA)H(+)(18C6), at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31 G* and M06/6-311+G(2d,2p)//B3LYP/6-31G* levels of theory. For all four (AcAA)H(+)(18C6) complexes, loss of neutral 18C6 corresponds to the most favorable dissociation pathway. At elevated energies, products arising from sequential dissociation of the primary CID product, H(+)(AcAA), are also observed. Protonated N(α)-AcLys exhibits a greater 18C6 binding affinity than other protonated N(α)-AcAAs, suggesting that the side chains of Lys residues are the preferred binding sites for 18C6 complexation to peptides and proteins. N(α)-AcLys exhibits a greater 18C6 binding affinity than N(ε)-AcLys, suggesting that binding of 18C6 to the side chain of Lys residues is more favorable than to the N-terminal amino group of Lys.

Comparison of the non-equilibrium predictions of Intrinsic Quantum Thermodynamics at the atomistic level with experimental evidence

Theoretical predictions from Intrinsic Quantum Thermodynamics (IQT) are compared to published experimental findings in order to examine whether or not calculations using IQT are consistent with experimental data. IQT makes the assertion that entropy is an intrinsic property of matter in the same way that inertial mass, energy, and momentum are and must, thus, exist even for single particles. Entropy as defined by IQT is a measure of the distribution of a system's internal energy at any given instant of time amongst the available internal degrees of freedom, i.e., the energy eigenlevels of the system. In this paper, it is shown that IQT models the internal relaxation of a 5-level rubidium system in a way that is consistent with the experimental data available in the literature. In addition, other experimental data found in the literature is compared with results obtained from the equation of motion of IQT that allows for heat interactions. It is shown that the decay of so-called "cat states" for single ions that are contained in Paul traps and that interact with a heat reservoir is also consistent with the calculations made using the theory of IQT.

Tuning of the Internal Energy and Isomer Distribution in Small Protonated Water Clusters H+(H2O)4–8: An Application of the Inert Gas Messenger Technique

Infrared spectroscopy of gas-phase hydrated clusters provides us much information on structures and dynamics of water networks. However, interpretation of spectra is often difficult because of high internal energy (vibrational temperature) of clusters and coexistence of many isomers. Here we report an approach to vary these factors by using the inert gas (so-called "messenger")-mediated cooling technique. Protonated water clusters with a messenger (M), H(+)(H(2)O)(4-8)·M (M = Ne, Ar, (H(2))(2)), are formed in a molecular beam and probed with infrared photodissociation spectroscopy in the OH stretch region. Observed spectra are compared with each other and with bare H(+)(H(2)O)(n). They show clear messenger dependence in their bandwidths and relative band intensities, reflecting different internal energy and isomer distribution, respectively. It is shown that the internal energy follows the order H(+)(H(2)O)(n) >> H(+)(H(2)O)(n)·(H(2))(2) > H(+)(H(2)O)(n)·Ar > H(+)(H(2)O)(n)·Ne, while the isomer-selectivity, which changes the isomer distribution in the bare system, follows the order H(+)(H(2)O)(n)·Ar > H(+)(H(2)O)(n)·(H(2))(2) > H(+)(H(2)O)(n)·Ne ~ (H(+)(H(2)O)(n)). Although the origin of the isomer-selectivity is unclear, comparison among spectra measured with different messengers is very powerful in spectral analyses and makes it possible to easily assign spectral features of each isomer.

Characteristics of positive and negative secondary ions emitted from [Formula: see text] and [Formula: see text] impacts.

The current limitation for SIMS analyses is insufficient secondary ion yields, due in part to the inefficiency of traditional primary ions. Massive gold clusters are shown to be a route to significant gains in secondary ion yields relative to other commonly used projectiles. At an impact energy of 520 keV, [Formula: see text] is capable of generating an average of greater than ten secondary ions per projectile, with some impact events generating >100 secondary ions. The capability of this projectile for signal enhancement is further displayed through the observation of up to seven deprotonated molecular ions from a single impact on a neat target of the model pentapeptide leu-enkephalin. Positive and negative spectra of leu-enkephalin reveal two distinct emission regimes responsible for the emission of either intact molecular ions with low internal energies or small fragment species. The internal energy distribution for this projectile is measured using a series of benzylpyridinium salts and compared with the small polyatomic projectile [Formula: see text] at 110 keV as well as distributions previously reported for electrospray ionization and fast atom bombardment. These results show that [Formula: see text] offers high secondary ion yields not only for small fragment ions, e.g. CN-, typically observed in SIMS analyses, but also for characteristic molecular ions. For the leu-enkephalin example, the yields for each of these species are greater than unity.

One- and Two-Dimensional Translational Energy Distributions in the Iodine-Loss Dissociation of 1,2-C2H4I2+ and 1,3-C3H6I2+: What Does This Mean?

Threshold photoelectron photoion coincidence (TPEPICO) has been used to study the sequential photodissociation reaction of internal energy selected 1,2-diiodoethane cations: C(2)H(4)I(2)(+) → C(2)H(4)I(+) + I → C(2)H(3)(+) + I + HI. In the first I-loss reaction, the excess energy is partitioned between the internal energy of the fragment ion C(2)H(4)I(+) and the translational energy. The breakdown diagram of C(2)H(4)I(+) to C(2)H(3)(+), i.e., the fractional ion abundances below and above the second dissociation barrier as a function of the photon energy, yields the internal energy distribution of the first daughter, whereas the time-of-flight peak widths yield the released translational energy in the laboratory frame directly. Both methods indicate that the kinetic energy release in the I-loss step is inconsistent with the phase space theory (PST) predicted two translational degrees of freedom, but is well-described assuming only one translational degree of freedom. Reaction path calculations partly confirm this and show that the reaction coordinate changes character in the dissociation, and it is, thus, highly anisotropic. For comparison, data for the dissociative photoionization of 1,3-diiodopropane are also presented and discussed. Here, the reaction coordinate is expected to be more isotropic, and indeed the two degrees of freedom assumption holds. Characterizing kinetic energy release distributions beyond PST is crucial in deriving accurate dissociative photoionization onset energies in sequential reactions. On the basis of both experimental and theoretical grounds, we also suggest a significant revision of the 298 K heat of formation of 1,2-C(2)H(4)I(2)(g) to 64.5 ± 2.5 kJ mol(-1) and that of CH(2)I(2)(g) to 113.5 ± 2 kJ mol(-1) at 298 K.

Collision Dynamics of O(3P) + DMMP Using a Specific Reaction Parameters Potential Form

Starting from previous benchmark CBS-QB3 electronic structure calculations (Conforti, P. F.; Braunstein, M.; Dodd, J. A. J. Phys. Chem. A 2009, 113, 13752), we develop two global potential energy surfaces for O((3)P) + DMMP collisions, using the specific reaction parameters approach. Each surface is simultaneously fit along the three major reaction pathways: hydrogen abstraction, hydrogen elimination, and methyl elimination. We then use these surfaces in classical dynamics simulations and compute reactive cross sections from 4 to 10 km s(-1) collision velocity. We examine the energy disposal and angular distributions of the reactive and nonreactive products. We find that for reactive collisions, an unusually large amount of the initial collision energy is transformed into internal energy. We analyze the nonreactive and reactive product internal energy distributions, many of which fit Boltzmann temperatures up to ~2000 K.

Sodium Cation Affinities of Commonly Used MALDI Matrices Determined by Guided Ion Beam Tandem Mass Spectrometry

The sodium cation affinities of six commonly used MALDI matrices are determined here using guided ion beam tandem mass spectrometry techniques. The collision-induced dissociation behavior of six sodium cationized MALDI matrices, Na+(MALDI), with Xe is studied as a function of kinetic energy. The MALDI matrices examined here include: nicotinic acid, quinoline, 3-aminoquinoline, 4-nitroaniline, picolinic acid, and 3-hydroxypicolinic acid. In all cases, the primary dissociation pathway corresponds to endothermic loss of the intact MALDI matrix. The cross section thresholds are interpreted to yield zero and 298 K Na+−MALDI bond dissociation energies (BDEs), or sodium cation affinities, after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and dissociation lifetimes. Density functional theory calculations at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* and MP2(full)/6-311+G(2d,2p)//B3LYP/6-31G* levels of theory are used to characterized the structures and energetics for these systems. The calculated BDEs exhibit very good agreement with the measured values for most systems. The experimental and theoretical Na+−MALDI BDEs determined here are compared with those previously measured by cation transfer equilibrium methods.

A pass too far: dissociation of internal energy selected paracyclophane cations, theory and experiment

The vacuum ultraviolet (VUV) photoionization and dissociative photoionization of three hydroxy-substituted [2.2]paracyclophane derivatives were studied yielding adiabatic ionization energies and dissociative photoionization energies (appearance energies). The simplest dissociation pathway is the breaking of both CH(2)-CH(2) bridge units and fragmenting the molecular ion in half to yield xylylene neutral and cationic fragments. The experimental data show that this process is outcompeted by a faster, higher energy channel, possibly yielding cyclooctatetraene derivatives. The role of the reaction coordinate, the effect of large amplitude motions on the density of states function at low and high energies and the temperature dependent 'population gap' in the internal energy distribution in large molecules are discussed in the context of applying statistical models to the dissociation. Computational approaches to the binding energy of paracyclophanes are marred with pitfalls. Noncovalent interactions play a major role in keeping paracyclophanes bound by some 200 kJ mol(-1) with respect to the two xylylene motifs, and the covalent CH(2)-CH(2) bonds are mostly counteracted by the geometric strain. The stabilizing effects are twofold: first, paracyclophanes are aromatic compounds, whereas xylylenes are not. Thus, the aromaticity of the molecule is induced by dimerization. Second, dispersive π-π interactions also stabilize the molecule. We evaluated 23 different computational chemistry approaches, and found that very few of the favorably scaling ones give an adequate description of this system. Among the DFT functionals tested, only PBE-D3 and perhaps M06-2X yielded consistently accurate results, comparable with MP3 and CCSD, or the G4 and CBS-QB3 composite methods. MP2 results in general suffer from significant overbonding.

Tautomerization in the formation and collision-induced dissociation of alkali metal cation-cytosine complexes

Noncovalent interactions between alkali metal cations and the various low-energy tautomeric forms of cytosine are investigated both experimentally and theoretically. Threshold collision-induced dissociation (CID) of M(+)(cytosine) complexes with Xe is studied using guided ion beam tandem mass spectrometry, where M(+) = Li(+), Na(+), and K(+). In all cases, the only dissociation pathway observed corresponds to endothermic loss of the intact cytosine molecule. The cross-section thresholds are interpreted to yield 0 and 298 K bond dissociation energies (BDEs) for the M(+)(cytosine) complexes after accounting for the effects of multiple ion-neutral collisions, the kinetic and internal energy distributions of the reactants, and dissociation lifetimes. Ab initio calculations are performed at the MP2(full)/6-31G* level of theory to determine the structures of the neutral cytosine tautomers, the M(+)(cytosine) complexes, and the TSs for unimolecular tautomerization. The molecular parameters derived from these structures are employed for the calculation of the unimolecular rates for tautomerization and the thermochemical analysis of the experimental data. Theoretical BDEs of the various M(+)(cytosine) complexes and the energy barriers for the unimolecular tautomerization of these complexes are determined at MP2(full)/6-311+G(2d,2p) level of theory using the MP2(full)/6-31G* optimized geometries. In addition, BDEs for the Li(+)(cytosine) complexes are also determined at the G3 level of theory. Based upon the tautomeric mixture generated upon thermal vaporization of cytosine, calculated M(+)-cytosine BDEs and barriers to tautomerization for the low-energy tautomeric forms of M(+)(cytosine), and measured thresholds for CID of M(+)(cytosine) complexes, we conclude that tautomerization occurs during both complex formation and CID.

Characterizing the Rovibrational Distribution of CD2CD2OH Radicals Produced via the Photodissociation of 2-Bromoethanol-d4

This work characterizes the internal energy distribution of the CD(2)CD(2)OH radical formed via photodissociation of 2-bromoethanol-d(4). The CD(2)CD(2)OH radical is the first radical adduct in the addition of the hydroxyl radical to C(2)D(4) and the product branching of the OH + C(2)D(4) reaction is dependent on the total internal energy of this adduct and how that energy is partitioned between rotation and vibration. Using a combination of a velocity map imaging apparatus and a crossed laser-molecular beam scattering apparatus, we photodissociate the BrCD(2)CD(2)OH precursor at 193 nm and measure the velocity distributions of the Br atoms, resolving the Br((2)P(1/2)) and Br((2)P(3/2)) states with [2 + 1] resonance enhanced multiphoton ionization (REMPI) on the imaging apparatus. We also detect the velocity distribution of the subset of the nascent momentum-matched CD(2)CD(2)OH cofragments that are formed stable to subsequent dissociation. Invoking conservation of momentum and conservation of energy and a recently developed impulsive model, we determine the vibrational energy distribution of the nascent CD(2)CD(2)OH radicals from the measured velocity distributions.

Communication: New insight into the barrier governing CO2 formation from OH + CO

Despite its relative simplicity, the role of tunneling in the reaction OH + CO → H + CO(2) has eluded the quantitative predictive powers of theoretical reaction dynamics. In this study a one-dimensional effective barrier to the formation of H + CO(2) from the HOCO intermediate is directly extracted from dissociative photodetachment experiments on HOCO and DOCO. Comparison of this barrier to a computed minimum-energy barrier shows that tunneling deviates significantly from the calculated minimum-energy pathway, predicting product internal energy distributions that match those found in the experiment and tunneling lifetimes short enough to contribute significantly to the overall reaction. This barrier can be of direct use in kinetic and statistical models and aid in the further refinement of the potential energy surface and reaction dynamics calculations for this system.