Excited Radicals Research Articles

Comparison of Atmospheric-Pressure He and Ar Plasma Jets Driven by Microsecond Pulses

In order to compare the characteristics of plasma jets in He and Ar, the plasma jets are driven by a home-made microsecond pulse power, which provides 0–30-kV output voltage with a rise time of 0.5 $\mu $ s and full-width at half-maximum of 4 $\mu $ s, and the pulse repetition frequency can be changed from single shot to 5 kHz. The main electrical parameters, such as applied voltage, total discharge current, and jet current, are measured. Results show that the intensity and length of jets become stronger and longer as the voltage increases. The discharge current of He plasma jet is only a few millamperes, whereas Ar plasma is hundreds of millamperes. For both cases, the jet speed is on an order of $\sim 10^{4}$ m/s estimated by the intensified charge coupled device images. The analysis shows that the differences between He and Ar plasma jets are mainly due to the physical and chemical characteristics of Ar and He gases, especially the different ionization energies of particles. In addition, the optical spectrum results show that there are more excited OH radicals and N2 of the second positive system in Ar plasma jet while the He plasma jet contains more excited O and N2+ of the first negative system.

Predicting the effect of angular momentum on the dissociation dynamics of highly rotationally excited radical intermediates.

We present a model which accurately predicts the net speed distributions of products resulting from the unimolecular decomposition of rotationally excited radicals. The radicals are produced photolytically from a halogenated precursor under collision-free conditions so they are not in a thermal distribution of rotational states. The accuracy relies on the radical dissociating with negligible energetic barrier beyond the endoergicity. We test the model predictions using previous velocity map imaging and crossed laser-molecular beam scattering experiments that photolytically generated rotationally excited CD2CD2OH and C3H6OH radicals from brominated precursors; some of those radicals then undergo further dissociation to CD2CD2 + OH and C3H6 + OH, respectively. We model the rotational trajectories of these radicals, with high vibrational and rotational energy, first near their equilibrium geometry, and then by projecting each point during the rotation to the transition state (continuing the rotational dynamics at that geometry). This allows us to accurately predict the recoil velocity imparted in the subsequent dissociation of the radical by calculating the tangential velocities of the CD2CD2/C3H6 and OH fragments at the transition state. The model also gives a prediction for the distribution of angles between the dissociation fragments' velocity vectors and the initial radical's velocity vector. These results are used to generate fits to the previously measured time-of-flight distributions of the dissociation fragments; the fits are excellent. The results demonstrate the importance of considering the precession of the angular velocity vector for a rotating radical. We also show that if the initial angular momentum of the rotating radical lies nearly parallel to a principal axis, the very narrow range of tangential velocities predicted by this model must be convoluted with a J = 0 recoil velocity distribution to achieve a good result. The model relies on measuring the kinetic energy release when the halogenated precursor is photodissociated via a repulsive excited state but does not include any adjustable parameters. Even when different conformers of the photolytic precursor are populated, weighting the prediction by a thermal conformer population gives an accurate prediction for the relative velocity vectors of the fragments from the highly rotationally excited radical intermediates.

Directional Propagation of Resistive-Barrier Discharge Above Water

A type of plasma discharge that propagates along the surface of a resistive barrier composed of an electrolyte in water is described. Electric fields parallel to the surface appear to steer the discharge in the direction of a submerged anode to produce a propagating plasma front that travels a distance of 20 cm or more along a trough, at a rate of $\sim 10~\mathrm{ms}^{\mathrm {-1}}$ . The plasma’s optical spectrum shows the presence of excited OH radicals, and the relatively high energy density of the plasma indicates possible usefulness for industrial applications.

Study of the time-resolved emission spectra of the ejected plume generated by ultrashort laser ablation of graphite

In this paper ultrashort laser pulses with different fluences (18 J/cm2-115 J/cm2) and pulse widths (50 fs-4 ps) are employed to ablate highly oriented pyrolytic graphite in vacuum (4×10-4 Pa). By recording the time-resolved emission spectra of the ablated plume, the ultrafast time evolution of the ablation process is investigated. The Swan bands of C2 radicals, the spectral band near 416 nm which may be assigned to the electronic transition from 1Σu+ to X1Σg+ of C15 clusters, and the emission continuum ranging from 370-700 nm are observed. From the recorded time-resolved emission spectra of the ablated plume, it is seen that at larger time delays only the emission continuum is observed. The decay process of the emission continuum of the plume generated by 50 fs, 115 J/cm2 laser pulses can be divided into a fast decreasing stage (before 20 ns time delay) and a slow decreasing stage (after 20 ns time delay), indicating that the emission continuum may come from two different compositions. During the fast decreasing process, the bremsstrahlung of the ablation-generated carbon plasma contributes to the major part of the continuum; while during the slow decreasing process, the thermal radiation of carbon clusters generated at a later stage of ablation mainly contributes to the continuum. In addition, the existence time of the continuum generated by 50 fs laser pulses increases with the decrease of laser fluence, indicating that laser pulses with lower fluences can generate more carbon clusters at later stages of ablation. It is also found that for the 50 fs pulses, when the laser fluence increases at the early stage of ablation, the quantities of carbon plasma and excited C2 radicals in the plume increase significantly, but the quantity of excited C15 radicals with larger mass only increases slightly. Therefore the laser fluence has a great impact on the concentrations of different compositions in the ejected plume, implying that different material removal mechanisms exist for ablation induced by laser pulses with different laser fluences. Finally, pulse width plays an important role in the time evolution manner of the emission continuum. As the laser pulse width increases, the two-stage decay process of the emission continuum gradually changes into one-stage process, indicating that the existence time intervals of carbon plasma and carbon clusters overlap each other for longer laser pulse width. And the whole evolution process of the emission continuum induced by 4 ps laser pulses is much slower than that induced by 50 fs laser pulses. Longer laser pulse width also causes the decrease of the spectral intensity of C2 radicals, and thus higher laser intensity favors the generation of excited C2 radicals.

Dual electron transfer pathways from the excited C60 radical anion: enhanced reactivities due to the photoexcitation of reaction intermediates.

In the present study, electron transfer (ET) processes from excited radical anions have been investigated using dyad molecules including C60. The deactivation process of excited C60˙(-), including the internal conversion from the D1 to the D0 state and the cooling process of the vibrationally hot ground state (D), was observed spectroscopically for the first time. These processes could be unambiguously distinguished by the observation of the stimulated emission from the D1 state. The intramolecular ET processes from the excited C60˙(-) were confirmed by the transient absorption spectra. Clearly, both D1 and D states acted as precursors for the ET, i.e., dual ET pathways were confirmed. The driving force dependence of the ET rates was well characterized by the Marcus theory, which revealed that the forward ET processes are located at the top region of the Marcus parabola. In addition, the ET from the excited imide radical anion to C60 and that from the ground state C60˙(-) to imide were examined. The ET rate from the excited imide radical anion and that from ground state C60˙(-) did not follow the Marcus parabola estimated for the ET from the excited C60˙(-). The observed difference can be attributed to the difference in the energy required to form the reduced spacer (Δ) in the superexchange mechanism. Because the Δ value tends to become smaller for ET processes from excited radical ions, fast and efficient ET processes are expected from these states as demonstrated in the present study.

Aqueous benzene-diols react with an organic triplet excited state and hydroxyl radical to form secondary organic aerosol

Chemical processing in atmospheric aqueous phases, such as cloud and fog drops, can play a significant role in the production and evolution of secondary organic aerosol (SOA). In this work we examine aqueous SOA production via the oxidation of benzene-diols (dihydroxy-benzenes) by the triplet excited state of 3,4-dimethoxybenzaldehyde, (3)DMB*, and by hydroxyl radical, ˙OH. Reactions of the three benzene-diols (catechol (CAT), resorcinol (RES) and hydroquinone (HQ)) with (3)DMB* or ˙OH proceed rapidly, with rate constants near diffusion-controlled values. The two oxidants exhibit different behaviors with pH, with rate constants for (3)DMB* increasing as pH decreases from pH 5 to 2, while rate constants with ˙OH decrease in more acidic solutions. Mass yields of SOA were near 100% for all three benzene-diols with both oxidants. We also examined the reactivity of atmospherically relevant mixtures of phenols and benzene-diols in the presence of (3)DMB*. We find that the kinetics of phenol and benzene-diol loss, and the production of SOA mass, in mixtures are generally consistent with rate constants determined in experiments containing a single phenol or benzene-diol. Combining our aqueous kinetic and SOA mass yield data with previously published gas-phase data, we estimate a total SOA production rate from benzene-diol oxidation in a foggy area with significant wood combustion to be nearly 0.6 μg mair(-3) h(-1), with approximately half from the aqueous oxidation of resorcinol and hydroquinone, and half from the gas-phase oxidation of catechol.

Optical emission spectra analysis of thermal plasma treatment of poly(vinyl chloride)

Abstract Decomposition of poly(vinyl chloride) (PVC) was investigated in radiofrequency thermal plasma in neutral, oxidative and reductive conditions. Optical emission spectroscopy (OES) was applied for the characterization of the plasma column. OES was used to identify active plasma components such as excited atoms, ions, radicals and molecules. The spectra were dominated by molecular C2, CN, OH, and CH bands, and atomic H, Ar, C, Cl and O lines. Emission intensities of main species were monitored versus various experimental parameters. The rotational-vibrational temperatures determined from different bimolecular species were considered in the range of 2000–6400 K. Solid soot samples were collected and purified to investigate the possibility of graphene formation as a by-product of the decomposition process.

Intermolecular and Intramolecular Electron Transfer Processes from Excited Naphthalene Diimide Radical Anions.

Excited radical ions are interesting reactive intermediates owing to powerful redox reactivities, which are applicable to various reactions. Although their reactivities have been examined for many years, their dynamics are not well-defined. In this study, we examined intermolecular and intramolecular electron transfer (ET) processes from excited radical anions of naphthalene-1,4,5,8-tetracarboxydiimide (NDI(•-)*). Intermolecular ET processes between NDI(•-)* and various electron acceptors were confirmed by transient absorption measurements during laser flash photolysis of NDI(•-) generated by pulse radiolysis. Although three different imide compounds were employed as acceptors for NDI(•-)*, the bimolecular ET rate constants were similar in each acceptor, indicating that ET is not the rate-determining step. Intramolecular ET processes were examined by applying femtosecond laser flash photolysis to two series of dyad compounds, where NDI was selectively reduced chemically. The distance dependence of the ET rate constants was described by a β value of 0.3 Å(-1), which is similar or slightly smaller than the reported values for donor-acceptor dyads with phenylene spacers. Furthermore, by applying the Marcus theory to the driving force dependence of the ET rate constants, the electronic coupling for the present ET processes was determined.

One protein, two chromophores: comparative spectroscopic characterization of 6,7-dimethyl-8-ribityllumazine and riboflavin bound to lumazine protein.

We investigated the lumazine protein from Photobacterium leiognathi in complex with its biologically active cofactor, 6,7-dimethyl-8-ribityllumazine, at different redox states and compared the results with samples containing a riboflavin cofactor. Using anaerobic photoreduction, we were able to record optical absorption kinetics from both cofactors in similar protein environments. It could be demonstrated that the protein is able to stabilize a neutral ribolumazine radical with ∼35% yield. The ribolumazine radical state was further investigated by W-band continuous-wave EPR and X-band pulsed ENDOR spectroscopy. Here, both the principal values of the g-tensor and an almost complete mapping of the proton hyperfine couplings (hfcs) could be obtained. Remarkably, the g-tensor's principal components are similar to those of the respective riboflavin-containing protein; however, the proton hfcs show noticeable differences. Comparing time-resolved optical absorption and fluorescence data from ribolumazine-containing samples, solely fluorescence but no signs of any intermediate radical or a triplet state could be identified. This is in contrast to lumazine protein samples containing the riboflavin cofactor, for which a high yield of the photogenerated triplet state and some excited flavin radical could be detected using time-resolved spectroscopy. These results clearly demonstrate that ribolumazine is a redox-active molecule and could, in principle, be employed as a cofactor in other enzymatic reactions.

Photoelectron-photofragment coincidence studies of the tert-butoxide anion (CH3)3CO((-)), the carbanion isomer (CH3)2CH2COH((-)), and corresponding radicals.

A study of the photodetachment and dissociative photodetachment (DPD) of the C(4)H(9)O(-) isomers tert-butoxide, (CH(3))(3)CO(-), and the α-hydroxy carbanion (CH(3))(2)C(CH(2))OH(-) is reported. Photoelectron-photofragment coincidence spectroscopy was used to study these anions at 387, 537, and 600 nm. Supported by CBS-QB3 ab initio calculations, the product mass and translational energy distributions were found to be consistent with dissociation of either highly excited (CH3)(3)CO radicals or (CH(3))(2)C(CH2)OH alkylhydroxy radicals. Vibrationally resolved photoelectron spectra of stable radicals at 537 and 600 nm in conjunction with Franck-Condon simulations were used to assign the dominant channel to tert-butoxide ((CH(3)3)CO(-)) anions thermalized to a vibrational temperature of 550 K. DPD is assigned to highly vibrationally excited radicals produced by photodetachment of unrelaxed tert-butoxide products formed at an effective source temperature of 1400 K. The higher energy carbanion was found to be a minor channel and was not observed to dissociate. Calculated energetics for photodetachment and DPD of (CH(3))(3)CO(-) and (CH(3))(2)C(CH(2))OH(-) are discussed and compared with the experimental results.

ChemInform Abstract: Rates and Energetics of Intramolecular Electron Transfer Processes in Conjugated Metallofullerenes

AbstractReview: 43 refs.

Characteristics of OH* Generation in Pin-to-Electrolyte Discharges

The locations of excited hydroxyl radical [OH (A-X), in short OH*] generation are observed using the highspeed images in low-voltage-driven pin-to-electrolyte discharges. A comparison of the emission from the plasma and OH* reveals that the generation site of OH* is depending on the electrolyte polarity. It implies that the difference of OH* properties with polarity can be due to the OH* generation pathways on the electrolyte surface and in the plasma volume, corresponding to the humidity, the electron temperature, and the quenching rate.

Kinetics of excited states and radicals in a nanosecond pulse discharge and afterglow in nitrogen and air**This paper is closely related to ‘Nitric oxide kinetics in the afterglow of a diffuse plasma filament’ by D Burnette et al (doi:10.1088/0963-0252/23/4/045007) published in this volume, which focuses on the kinetic modelling of the experiments. This paper presents the results of the experiments.

The present kinetic modelling calculation results provide key new insights into the kinetics of vibrational excitation of nitrogen and plasma chemical reactions in nanosecond pulse, ‘diffuse filament’ discharges in nitrogen and dry air at a moderate energy loading per molecule, ∼0.1 eV per molecule. It is shown that it is very important to take into account Coulomb collisions between electrons because they change the electron energy distribution function and, as a result, strongly affect populations of excited states and radical concentrations in the discharge. The results demonstrate that the apparent transient rise of N2 ‘first level’ vibrational temperature after the discharge pulse, as detected in the experiments, is due to the net downward V–V energy transfer in N2–N2 collisions, which increases the N2(X 1Σ, v = 1) population. Finally, a comparison of the model's predictions with the experimental data shows that NO formation in the afterglow occurs via reactive quenching of multiple excited electronic levels of nitrogen molecule, , by O atoms.

The vitiation effects of water vapor and carbon dioxide on the autoignition characteristics of kerosene

In ground tests of hypersonic scramjet, the high-enthalpy airstream produced by burning hydrocarbon fuels often contains contaminants of water vapor and carbon dioxide. The contaminants may change the ignition characteristics of fuels between ground tests and real flights. In order to properly assess the influence of the contaminants on ignition characteristics of hydrocarbon fuels, the effect of water vapor and carbon dioxide on the ignition delay times of China RP-3 kerosene was studied behind reflected shock waves in a preheated shock tube. Experiments were conducted over a wider temperature range of 800–1 500K, at a pressure of 0.3 MPa, equivalence ratios of 0.5 and 1, and oxygen concentration of 20%. Ignition delay times were determined from the onset of the excited radical OH emission together with the pressure profile. Ignition delay times were measured for four cases: (1) clean gas, (2) gas vitiated with 10% and 20% water vapor in mole, (3) gas vitiated with 10% carbon dioxide in mole, and (4) gas vitiated with 10% water vapor and 10% carbon dioxide, 20% water vapor and 10% carbon dioxide in mole. The results show that carbon dioxide produces an inhibiting effect at temperatures below 1 300 K when ϕ = 0.5, whereas water vapor appears to accelerate the ignition process below a critical temperature of about 1 000 K when ϕ = 0.5. When both water vapor and carbon dioxide exist together, a minor inhibiting effect is observed at ϕ = 0.5, while no effect is found at ϕ = 1.0. The results are also discussed preliminary by considering both the combustion reaction mechanism and the thermophysics properties of the fuel mixtures. The current measurements demonstrate vitiation effects of water vapor and carbon dioxide on the autoignition characteristics of China RP-3 kerosene at air-like O2 concentration. It is important to account for such effects when data are extrapolated from ground testing to real flight conditions.

Reactions of 5-methylcytosine cation radicals in DNA and model systems: Thermal deprotonation from the 5-methyl group vs. excited state deprotonation from sugar

Purpose: To study the formation and subsequent reactions of the 5-methyl-2′-deoxycytidine cation radical (5-Me-2′-dC•+) in nucleosides and DNA-oligomers and compare to one-electron oxidized thymidine.Materials and methods: Employing electron spin resonance (ESR), cation radical formation and its reactions were investigated in 5-Me-2′-dC, thymidine (Thd) and their derivatives, in fully double-stranded (ds) d[GC*GC*GC*GC*]2 and in the 5-Me-C/A mismatched, d[GGAC*AAGC:CCTAATCG], where C* = 5-Me-C.Results: We report 5-Me-2′-dC•+ production by one-electron oxidation of 5-Me-2′-dC by Cl2•− via annealing in the dark at 155 K. Progressive annealing of 5-Me-2′-dC•+ at 155 K produces the allylic radical (C-CH2•). However, photoexcitation of 5-Me-2′-dC•+ by 405 nm laser or by photoflood lamp leads to only C3′• formation. Photoexcitation of N3-deprotonated thyminyl radical in Thd and its 5′-nucleotides leads to C3′• formation but not in 3′-TMP which resulted in the allylic radical (U-CH2•) and C5′• production. For excited 5-Me-2′,3′-ddC•+, absence of the 3′-OH group does not prevent C3′• formation. For d[GC*GC*GC*GC*]2 and d[GGAC*AAGC:CCTAATCG], intra-base paired proton transferred form of G cation radical (G(N1-H)•: C(+ H+)) is found with no observable 5-Me-2′-dC•+ formation. Photoexcitation of (G(N1-H)•:C(+ H+)) in d[GC*GC*GC*GC*]2 produced only C1′• and not the expected photoproducts from 5-Me-2′-dC•+. However, photoexcitation of (G(N1-H)•:C(+ H+)) in d[GGAC*AAGC:CCTAATCG] led to C5′• and C1′• formation.Conclusions: C-CH2• formation from 5-Me-2′-dC•+ occurs via ground state deprotonation from C5-methyl group on the base. In the excited 5-Me-2′-dC•+ and 5-Me-2′,3′-ddC•+, spin and charge localization at C3′ followed by deprotonation leads to C3′• formation. Thus, deprotonation from C3′ in the excited cation radical is kinetically controlled and sugar C-H bond energies are not the only controlling factors in these deprotonations.

Multi-photon and electron impact ionisation studies of reactivity in adenine–water clusters

Multi-photon ionisation (MPI) and electron impact ionisation (EII) mass spectrometry experiments have been carried out to probe unimolecular and intermolecular reactivities in hydrated adenine clusters. The effects of clustering with water on fragment ion production from adenine have been studied for the first time. While the observation of NH4+ fragments indicated the dissociation of protonated adenine, the dominant hydration effects were enhanced C4H4N4+ production and the suppression of dissociative ionisation pathways with high activation energies. These observations can be attributed to energy removal from the excited adenine radical cation via cluster dissociation. Comparisons of MPI and EII measurements provided the first experimental evidence supporting hypoxanthine formation in adenine–water clusters via theoretically predicted barrierless deamination reactions in closed shell complexes.

Radical species generation and their lifetime extension by a femtosecond and nanosecond dual-laser system

For many material processes, desired radical species at excited states are produced which interact with a given substrate for a certain period of time allowing chemical reactions between them to occur and complete. Hence, it is important to maintain the population of the excited radical species for an extended period of time, i.e., their lifetime, which is defined as the time for emission intensity to decay to 1/e of the initial intensity. In this study, a femtosecond–nanosecond (fs–ns) dual-laser system was employed to generate desired radical species via the fs laser and, then, to extend the lifetime of the radical species by the ns laser with different time delays between the two fs–ns laser pulses. The proposed method is demonstrated for a N2–CO2 mixture with CN as the radical species. The results show that the lifetime of CN radical species can be significantly extended, particularly the (3, 3) spectral line which was extended from 30 to 200 ns. By using a wavelength-tunable ns laser, the lifetime of most radical species can be extended which may increase the process efficiency for many material processes.

Imaging and Scattering Studies of the Unimolecular Dissociation of the BrCH2CH2O Radical from BrCH2CH2ONO Photolysis at 351 nm

We report a study of the unimolecular dissociation of BrCH2CH2O radicals produced from the photodissociation of BrCH2CH2ONO at 351/355 nm. Using both a crossed laser-molecular beam scattering apparatus with electron bombardment detection and a velocity map imaging apparatus with tunable VUV photoionization detection, we investigate the initial photodissociation channels of the BrCH2CH2ONO precursor and the subsequent dissociation of the vibrationally excited BrCH2CH2O radicals. The only photodissociation channel of the precursor we detected upon photodissociation at 351 nm was O-NO bond fission. C-Br photofission and HBr photoelimination do not compete significantly with O-NO photofission at this excitation wavelength. The measured O-NO photofission recoil kinetic energy distribution peaks near 14 kcal/mol and extends from 5 to 24 kcal/mol. There is also a small signal from lower kinetic energy NO product (it would be 6% of the total if it were also from O-NO photofission). We use the O-NO photofission P(ET) peaking near 14 kcal/mol to help characterize the internal energy distribution in the nascent ground electronic state BrCH2CH2O radicals. At 351 nm, some but not all of the BrCH2CH2O radicals are formed with enough internal energy to unimolecularly dissociate to CH2Br + H2CO. Although the signal at m/e = 93 (CH2Br(+)) obtained with electron bombardment detection includes signal both from the CH2Br product and from dissociative ionization of the energetically stable BrCH2CH2O radicals, we were able to isolate the signal from CH2Br product alone using tunable VUV photoionization detection at 8.78 eV. We also sought to investigate the source of vinoxy radicals detected in spectroscopic experiments by Miller and co-workers ( J. Phys. Chem. A 2012 , 116 , 12032 ) from the photodissociation of BrCH2CH2ONO at 351 nm. Using velocity map imaging and photodissociating the precursor at 355 nm, we detected a tiny signal at m/e = 43 and a larger signal at m/e = 15 that we tentatively assign to vinoxy. An underlying signal in the time-of-flight spectra at m/e = 29 and m/e = 42, the two strongest peaks in the literature electron bombardment mass spectrum of vinoxy, is also apparent. Comparison of those signal strengths with the signal at HBr(+), however, shows that the vinoxy product does not have HBr as a cofragment, so the prior suggestion by Miller and co-workers that the vinoxy might result from a roaming mechanism is contraindicated.

Vibrational Nonequilibrium in the Hydrogen-Oxygen Reaction at Different Temperatures

A theoretical model of chemical and vibrational kinetics of hydrogen oxidation is suggested based on the consistent account for the vibrational nonequilibrium of HO2 radical which forms in result of bimolecular recombination H + O2 = HO2 in the vibrationally excited state. The chain branching H + O2 = O + OH and inhibiting H + O2 + M = HO2 + M formal reactions are considered (in the terms of elementary processes) as a general multi-channel process of forming, intramolecular energy redistribution between modes, relaxation, and monomolecular decay of the comparatively long-lived vibrationally excited HO2 radical which is capable to react and exchange of energy with another components of the mixture. The model takes into account the vibrational nonequilibrium for the starting (primary) H2 and O2 molecules, as well as the most important molecular intermediates HO2, OH, O2(1D), and the main reaction product H2O. The calculated results are compared with the shock tube experimental data for strongly diluted H2-O2 mixtures at 1000 T p 2 radical acts as a key intermediate in the principally important chain branching process. For T 2 radical is the essence of this process.

Spectroscopy and dynamics of the HOCO radical: insights into the OH + CO → H + CO2 reaction.

After more than forty years of scrutiny, crucial new details regarding the elementary reaction OH + CO → H + CO2 are still emerging from experimental and theoretical studies of the HOCO radical intermediate. In this perspective, previous studies of this elementary reaction and the structure and energetics of the HOCO radical will be briefly reviewed. Particular attention will be paid to the experimental techniques used in our laboratory to prepare excited HOCO radicals by both photodetachment and dissociative photodetachment of HOCO(-). These experiments directly probe the dynamics occurring on the ground and excited states of the HOCO radical, and are sensitive to both direct and tunneling-induced dissociation. Photoelectron-photofragment coincidence experiments on HOCO(-) in particular have been used to study tunneling from the HOCO well to form H + CO2 products. In addition, new experimental insights into the OH + CO entrance channel for the reaction will be presented. These studies have provided a number of constraints on the potential energy surface for this system from an energetic and dynamical perspective, and have helped spur a renewed effort to characterize the global potential energy surface and reaction dynamics of this fundamental chemical reaction. Outstanding questions and new directions for future work on the HOCO radical will be discussed.