Minor Channel Research Articles

THEORETICAL RESEARCH ON THE REACTION MECHANISM OF O + HCNO

We apply a theoretical method to study the O + HCNO reaction, in which the products Pi with i = 1, 2, …, 8 are involved. It is carried out by means of CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p) + ZPVE computational method to detect a set of reasonable pathways. It shows that P5(H + NO + CO) and P8(HON + CO) are both the major product channel; in addition, there are some degrees of contributions from P1(HCO + NO) to form P5(H + NO + CO) ; P4(NH + CO2) is considered a minor product channel, and there are some degrees of contributions from P2(HNO + CO) to form P4(NH + CO2) ; whereas the other three channels, P3(NCO + OH) , P6(CNO + OH) , and P7(HCN + O2) are less favorable or even unfavorable. All these theoretical results are in harmony with the experimental facts.

First-principles theoretical studies of half-metallic ferromagnetism in CrTe

Using full-potential linear augmented plane-wave method (FP-LAPW) we have studied the stability and electronic properties of the chalcogenide CrTe in three competing structures: rocksalt (RS), zinc blende (ZB), and the NiAs-type (NA) hexagonal. Although the ground state is of NA structure, RS and ZB are interesting in that these fcc-based structures, which can perhaps be grown on various semiconductor substrates, exhibit half-metallic (HM) phases above some critical values of the lattice parameter. We find that the NA structure is not HM at its equilibrium volume while both ZB and RS structures are. The RS structure is more stable than the ZB with an energy that is lower by 0.25 eV/atom. While confirming previous results on the HM phase in ZB structure, we provide hitherto unreported results on the HM RS phase, with a gap in the minority channel and a magnetic moment of $4.0\text{ }{\ensuremath{\mu}}_{B}/\text{f}\text{.u}\text{.}$ A comparison of total energies for the ferromagnetic (FM), nonmagnetic, and antiferromagnetic (AFM) configurations shows the lowest energy configuration to be FM for CrTe in all the three structures. The exchange interactions in the RS and ZB structures are studied for a wide range of the lattice parameter using the linear-response method and a mapping of the total energy to the classical Heisenberg model. These linear-response calculations are performed in the linear muffin-tin orbitals (LMTOs) basis, using the atomic sphere approximation (ASA). We have verified that the results of the electronic structure obtained via the LMTO-ASA method under local-density approximation (LDA) and $\text{LDA}+U$ schemes are in close agreement with those obtained via the more accurate FP-LAPW method. The results show that the exchange interactions in the RS structure are much more short ranged than in the ZB structure. Hence, for the RS structure the exchange interactions are also studied by using a nearest- and next-nearest-neighbor $({J}_{1}\text{\ensuremath{-}}{J}_{2})$ model and the energy differences between FM and two AFM states. These ${J}_{1}\text{\ensuremath{-}}{J}_{2}$ model results are obtained by using both the FP-LAPW and LMTO-ASA methods and compared with the linear-response results. The calculated Curie temperatures for the RS phase are consistently higher than those for the ZB phase.

Theoretical studies on the reactions CH3SCH3 with OH, CF3, and CH3 radicals

The multiple-channel reactions OH + CH(3)SCH(3) → products, CF(3) + CH(3)SCH(3) → products, and CH(3) + CH(3)SCH(3) → products are investigated by direct dynamics method. The optimized geometries, frequencies, and minimum energy path are all obtained at the MP2/6-31+G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for eight reaction channels are calculated by the improved canonical variational transition state theory with small-curvature tunneling contribution over the temperature range 200-3000 K. The total rate constants are in good agreement with the available experimental data and the three-parameter expressions k(1) = 4.73 × 10(-16)T(1.89) exp(-662.45/T), k(2) = 1.02 × 10(-32)T(6.04) exp(933.36/T), k(3) = 3.98 × 10(-35)T(6.60) exp(660.58/T) (in unit of cm(3) molecule(-1) s(-1)) over the temperature range of 200-3000 K are given. Our calculations indicate that hydrogen abstraction channels are the major channels and the others are minor channels over the whole temperature range.

The role of ultrathin AlN barrier in the reduction in the hot electron and self-heating effects for GaN-based double-heterojunction high electron mobility transistors

We propose an AlN/GaN/InGaN/GaN double-heterojunction high electron mobility transistor (DH-HEMT) structure with a 4 nm thin AlN barrier layer. The performance of the DH-HEMT device is investigated by using two-dimensional numerical simulation. The conduction band profile is obtained by using the Poisson’s equation and Fermi–Dirac statistics in combination with the polarization charges. Due to large conduction-band offset of the AlN/GaN interface and strong polarization of AlN, the minor channel at GaN/InGaN interface can be eliminated. Further, the hot electron and self-heating effects on the transport properties of this DH-HEMT are investigated by using hydrodynamic model. In comparison with the AlGaN barrier DH-HEMT and conventional HEMT, this kind of DH-HEMT can effectively reduce the hot electron effect under high voltage. The reason is that the maximum field strength is far below the critical value for the existence of the hot electron effect in the AlGaN barrier DH-HEMTs and conventional HEMTs with the same voltage 6 V. The simulation results also show that the ultrathin AlN barrier layer can significantly reduce thermal impedance, and then lower the self-heating effect. Furthermore, the passivation layer has significant role in the self-heating effect of the ultrathin barrier DH-HEMTs.

The synthesis and spectroscopic characterization of poly( p-phenylene ethynylene) with 3-connected BODIPY end groups

A novel 3-connected BODIPY end-capped poly( p-phenylene ethynylene) and a matching model compound were synthesized by palladium-catalyzed cross-coupling reaction. The structures were confirmed using 1H NMR, UV–vis spectrophotometry and fluorescence spectroscopy. Both the polymer and the model compound showed absorption and emission bands characteristic for the BODIPY chromophore and the p-phenylene ethynylene linker. However, while upon excitation of the p-phenylene ethynylene linker energy transfer occurs for nearly 100% in the model compound, it is only a minor decay channel of the singlet excited state of the p-phenylene ethynylene linker in the polymer.

A density functional investigation of the reaction mechanism of H2O + HCNO

A theoretical investigation of the H2O + HCNO reaction, which is carried out by means of CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPVE computational method to determine a set of reasonable pathways, there are seven product pathways, Pi with i = 1, 2, …, 7 are involved. It is shown that P1(H2O + NCOH), P2(CO + NH2 + OH), P4(HCN + HO2 + H), and P6(CO + NH2OH) are the major product channels; and P7(HOC + H2 + NO) is the minor product channels, whereas the other channels for P3(HNO + HCOH) and P5(HNO + H2CO) are very minor, the minor product channels. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011

Quantum conductance of a single magnetic atom: Anab initiostudy

Our ab initio study explains recent puzzling experiments on the conductance of a single Co adatom deposited either on Cu(111) or on ferromagnetic Co islands and contacted with both magnetic and nonmagnetic electrodes [N. N\'eel, J. Kr\"oger, and R. Berndt, Phys. Rev. Lett. 102, 086805 (2009)]. We provide clear evidence that the conductance of a single atomic junction in the contact regime is close to ${G}_{0}/2$ (${G}_{0}$ is the quantum of conductance) for ferromagnetic electrodes and to ${G}_{0}$ for nonmagnetic ones. Spin-dependent calculations reveal that a conductance of ${G}_{0}/2$ originates from a combination of partially open majority and minority channels. The bonding between the Co adatom and the Co island reduces significantly the contribution of the minority $d$ electrons to the conductance, leading to the observation of half-integer conductance.

Flexibility analysis of irrigation outlet structures using simulation of irrigation canal hydrodynamic model

The Upper Swat Canal (USC) System became operational in 1917-1918 in North West Frontier Province (NWFP) of Pakistan. The rehabilitation and modernization of the USC was undertaken with a view to overcoming the shortage of water supplies for irrigation. The water allowance was enhanced from 0.39 to 0.77 Ls -1 ha -1 in the study area. Recently, the operation and management of a secondary canal or 'distributary' was transferred to the Farmers Organization (FO). This distributary named 'Chowki' offtakes from the Maira Branch of the USC. The cultivable command area (CCA) of this distributary is 4,306 ha and it serves 1,485 beneficiaries. A management committee on Chowki Distributary was formed in 2003. This distributary consists of one main and two minor channels having twenty-eight direct outlets. The Simula- tion of Irrigation Canal (SIC) hydrodynamic model was used to evaluate the flexibility of Chowki Distributary. The model was calibrated at 100, 80 and 70% of the design discharge (Qd) and it was validated at 90, 85 and 60% of the design discharge. The observed and simulated water levels were in close agreement with each other for the calibration and validation periods. The statistical analysis and paired t-test indicate that the model results are not statistically different from the measured values at 1% sig- nificance level. The simulated results of the SIC model were applied to studying flexibility of the outlet structures along the Chowki Distributary. The flexibility analysis demonstrates that poor performance is inbuilt into the system due to inadequate control over the accuracy of the crest setting during the construction of the outlets.

Observations of the Florida and Yucatan Currents from a Caribbean Cruise Ship

AbstractThe Yucatan and Florida Currents represent the majority of the warm-water return path of the global thermohaline circulation through the tropical/subtropical North Atlantic Ocean. Their transports are quantified and compared by analyzing velocity data collected aboard the cruise ship Explorer of the Seas. From 157 crossings between May 2001 and May 2006, the mean transport of the Florida Current at 26°N was estimated to be 30.8 ± 3.2 Sv (1 Sv ≡ 106 m3 s−1), with seasonal amplitude of 2.9 Sv. Upstream, the Yucatan Current was estimated from 90 crossings to be 30.3 ± 5 Sv, with seasonal amplitude of 2.7 Sv. These two currents are shown to be linked at seasonal time scales. Hence, contrary to former results, it was found that transports through the Florida Straits and the Yucatan Channel are similar, with the implication that only small inflows occur through minor channels between them.

Variable Electron and Neutral Density Attachment Mass Spectrometry: Temperature-Dependent Kinetics of Electron Attachment to PSCl3 and PSCl2 and Mutual Neutralization of PSCl2− and PSCl− with Ar+

We describe the VENDAMS (variable electron and neutral density attachment mass spectrometry) technique to measure the rate constants of various processes occurring as primary, secondary, and higher order chemistry in a flowing afterglow at high charge densities over a temperature range of 300 to 550 K. In particular, we report measurements of rate constants of ion-ion mutual neutralization and electron attachment to radical species, processes which have proven difficult to study through other means. The product negative ion abundances from the addition of PSCl(3) to an Ar(+)/e(-) plasma have been measured as a function of initial electron densities between 1 × 10(8) and 4 × 10(10) cm(-3). Data at lower electron densities yield branching ratios of the primary electron attachment to PSCl(3); determination of the reactions and rate constants occurring at low electron densities then allows for determination of the greater number of reactions and rate constants contributing at higher electron densities. Reaction rate constants and branching ratios of electron attachment to PSCl(2) are reported; this is the first measurement of electron attachment to a radical as a function of temperature. The data show an unusual negative temperature dependence; however, a zero or even slightly positive dependence is within the uncertainty. Measured electron attachment rate constants are 1.4 × 10(-7), 1.1 × 10(-7), and 9.1 × 10(-8) ± 40% cm(3) s(-1) at 300, 400, and 550 K, respectively; the dominant product channel is PSCl + Cl(-) (95, 87, and 77% at 300, 400, and 550 K), and the minor channel is PSCl(-) + Cl. Ion-ion mutual neutralization rate constants of both PSCl(-) and PSCl(2)(-) with Ar(+) are reported over the investigated temperature range; rate constants at 300 K are 4.9 × 10(-8) ± 20% cm(3) s(-1) and 4.5 × 10(-8) ± 15% cm(3) s(-1) and show temperature dependences of T(-0.5±0.3) and T(-0.9±0.3), respectively.

Electron attachment to sulfur oxyhalides: SOF2, SOCl2, SO2F2, SO2Cl2, and SO2FCl attachment rate coefficients, 300–900 K

Electron attachment to SOF(2), SOCl(2), SO(2)F(2), SO(2)FCl, and SO(2)Cl(2) was studied with two flowing-afterglow Langmuir-probe apparatuses over the temperature range 300-900 K. Attachment rate coefficients at 300 K are k(a) = 2.6+/-0.8x10(-10)(SOF(2)), 1.8+/-0.5x10(-8)(SOCl(2)), 4.8+/-0.7x10(-10)(SO(2)F(2)), 2.4+/-0.7x10(-9)(SO(2)Cl(2)), and 2.0+/-0.6x10(-7) cm(3) s(-1)(SO(2)FCl). Arrhenius plots of the data imply activation energies of 56+/-22 meV(SOF(2)), 92+/-40(SO(2)F(2)), 44+/-22 meV(SOCl(2)), and 29+/-15 meV(SO(2)Cl(2)). The rate coefficients for SO(2)FCl decrease slightly with temperature, commensurate with the decrease in the capture rate coefficient. Electron attachment to SOF(2) and SO(2)F(2) is nondissociative, while reaction with SOCl(2), SO(2)FCl, and SO(2)Cl(2) is dissociative. Dissociative attachment is dominated by channels arising from S-Cl bond cleavage but also includes a minor channel forming a dihalide product ion. Branching fraction data are reported for the dissociative attachment channels.

Reaction mechanism of CHCl − + CSO: A theoretical study

The doublet potential energy surface (PES) for the reaction of CHCl − with CSO is explored at the B3LYP/6-311++G(d,p), B3LYP/6-311++G(3df,2p) and CCSD(T)/6-311++G(3df,2p) (single-point) levels. Various possible reaction pathways are probed. It is shown that the most favorable association between CHCl − and CSO is found to be middle-C attack forming CHClC(O)S − 1 with no barrier. Starting from 1, the most feasible pathway is the concerted S-shift along with Cl-extrusion of 1 to form product P 2 (Cl − + SCHCO). The minor product channel is the concerted O-shift along with Cl-extrusion of 1 to generate product P 1 (Cl − + OCHCS). Further conversions of P 1 may form P 6 (SCHCl − + CO). Because the isomers and transition states involved in the feasible pathways all lie below the reactant, the title reaction is expected to proceed very fast which is consistent with the measured large rate constant in experiment. Our calculated results may be helpful for understanding the mechanism of the title reaction.

OH Radical Initiated Oxidation of 1,3-Butadiene: Isomeric Selective Study of the Dominant Addition Channel

We report the first isomeric selective kinetic study of the dominant isomeric pathway in the OH initiated oxidation of 1,3-butadiene in the presence of O(2) and NO using the laser photolysis-laser induced fluorescence (LP-LIF) technique. The photodissociation of the precursor 2-iodo-but-3-en-1-ol results exclusively in the dominant OH-butadiene addition product, permitting important insight into the OH initiated oxidation mechanism. On the basis of analysis of the time dependent OH/OD signals, we have determined a rate constant for O2 addition to the hydroxyalkyl radical of 7.0(-3.0)(+7.0) x 10(-13) cm(3) s(-1), and we find a value of 1.5(-0.6)(+1.0) x 10(-11) cm(3) s(-1) for the overall reaction rate constant of the hydroxy peroxy radical with NO. We also report the first clear experimental evidence of the (E) form of the delta-hydroxyalkoxy channel through isotopic labeling experiments and provide an upper bound of 13 +/- 5% to its branching ratio. This species provides a mechanistic pathway for the formation of 4-hydroxy-2-butenal, which has been identified as a first generation end product. This isomeric selective kinetic study, together with a previous study on the minor channel of the 1,3-butadiene oxidation, yields a comprehensive picture of butadiene oxidation under high NOx conditions relevant to most regions in the continental US.

Quantum Interference in NO2

This paper investigates the origin of a quantum interference observed when NO(2) is dissociatively ionized by short pulses of ultraviolet light. We describe time-resolved measurements of NO(+), O(+), and NO(2)(+) ions produced following the interaction of NO(2) with a approximately 70 fs duration pulse centered close to 400 nm and a subsequent time-delayed probe pulse close to 269, 205, or 400 nm. A quantum beat oscillation with a period of 524 fs and a characteristic damping time of 8 ps is observed on all transient ion signals. We investigate the effect of tuning the central wavelength of the excitation pulse over a 12 nm range, and we discuss the potential importance of three possible multiphoton pathways involving one, two, and three pump photons. We conclude that the ionization pathway responsible for the beat signal is most likely due to a process involving the absorption of two pump photons and two probe photons. This presents an interesting problem with respect to the interpretation of the mechanism responsible for the quantum interference signature since the electronic states of NO(2) reached at the two-photon level are all thought to be extremely short-lived and to dissociate on a time scale that is far shorter than the characteristic damping time of the oscillatory signals. We suggest that a possible explanation for the observed dynamics is associated with a minor dissociation channel of the (2)(2)B(2) state of NO(2) through its interaction with the longer lived (2)(2)A(1) state.

The Ultrafast Dynamics of Electronic Excitations in Pentacene Thin Films

AbstractPentacene films which are model systems for organic electronics exhibit contrary to the pentacene monomer extremely little photoluminescence. This points to an ultrafast relaxation mechanism. We apply pump-probe absorption spectroscopy with a time resolution of 30 fs to microcrystalline pentacene films. It is found that the primarily excited Frenkel excitons decay within 70 fs to a non fluorescing singlet species. Contrary to expectations fission into triplets is only a minor channel. We propose that the ultrafast relaxation of the photoexcited excitons leads to a species very similar to excimers. The radiative transition of the excimer to the ground state is electric dipole forbidden due to symmetry reasons. The excimer formation provides therefore an efficient mechanism to turn off the emission.

A study of fold characteristics and deformation style using the evolution of the land surface: Zagros Simply Folded Belt, Iran

Abstract Deformation styles within a fold–thrust belt can be understood in terms of the spatial organization and geometry of the fold structures. In young fold–thrust belts such as the Zagros, this geometry is reflected topographically by concordant landform morphology. Thus, the distribution of deformation structures can be characterized using satellite image analysis, digital elevation models, the drainage network and geomorphological indicators. The two distinct fold types considered in this study (fault-bend folds and detachment folds) both trending NW–SE, interact with streams flowing NE–SW from the High Zagros Mountains into the Persian Gulf. Multiple abandoned stream channels cross fault-bend folds related to deep-seated thrust faults. In contrast, detachment folds, which propagate laterally relatively rapidly, are characterized by diverted major stream channels and dendritic minor channels at the fold tips. Thus these two fold types can be differentiated on the basis of their geometry (fault-bend folds, being long, linear and asymmetrical, can be distinguished from detachment folds, which tend to be shorter and symmetrical) and on their associated geomorphological structures. The spatial organization of these structures in the Zagros Simply Folded Belt indicates that deformation is the result of the interaction of footwall collapse and the associated formation of long, linear fault-bend folds, and serial folding characterized by relatively short periclinal folds. Footwall collapse occurs first, followed by serial folding to the NE (i.e. in the hanging wall of the fault-bend folds), often on higher detachments within the sediment pile.

Dissociation of copper(ii) ternary complexes containing cystine

The collision-induced dissociations are reported for Cu(II) complexes containing 1,4,7-triazacyclononane (tacn) as the auxiliary ligand and a peptide containing one cystine residue. For six of the complexes examined, cleavage of the S-S bond in the peptide was the dominant fragmentation pathway. The exceptions were for complexes containing the largest peptides, (GlyCys'Gly)(2) and (GlyGlyCys')(2) (Cys' = NHCH(CH(2)S)CO, one half of the cystine residue; terminal H and OH are implicit), for which proton transfer to the auxiliary ligand was the major channel. Cleavage of the C-S bond was observed, but was a minor channel for all complexes. The radical cation (Cys')(2)(*+) was not observed although the complementary ion [Cu(I)(tacn)](+) was present in moderate abundance. Density functional calculations (at B3LYP/6-311++G(d,p)) gave low barriers to fragmentation of (Cys')(2)(*+) by homolytic fission of the C-S bond of the canonical ion (barrier 16.5 kcal mol(-1)) and of the structure at the global minimum, a captodative ion (barrier 17.2 kcal mol(-1)). Peptide radical cations (GlyCys')(2)(*+), (GlyCys'Gly)(2)(*+), (GlyGlyCys')(2)(*+) and (GlyCys'(Cys')Gly)(*+) were observed in low abundances; the first two of these ions dissociated predominantly by fragmentation of the S-S bond, while the other two preferentially cleaved at an amide bond. No cleavage of the C-S bond was observed for the peptide radical cations. Density functional calculations at B3LYP/6-31G(d) established that the cystine in [Cu(II)(tacn)(Cys')(2)](*2+) is bound as a zwitterion through the carboxylate anion with the proton on the distal amino group. The lowest energy complex containing a canonical cystine, coordinated through the carbonyl oxygen and the amino group of the same Cys', is 8.3 kcal mol(-1) higher in enthalpy.

Nitrogen dioxide reactions with atomic lanthanide cations and their monoxides: gas-phase kinetics at room temperature

Results of experimental investigations are reported for the gas-phase kinetics of chemical reactions between nitrogen dioxide (NO(2)) and 14 different atomic cations of the lanthanide series, Ln(+) (Ln = La-Lu, excluding Pm), and their monoxides, LnO(+). Measurements were taken with an inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer in helium buffer-gas at a pressure of 0.35 +/- 0.01 Torr and at 295 +/- 2 K. The atomic lanthanide cations were produced at ca. 5500 K in an ICP source and allowed to decay radiatively and to thermalize by collisions with Ar and He atoms prior to reaction with NO(2). The atomic ions were observed to react rapidly with NO(2) with large rate coefficients, k > 2 x 10(-10) cm(3) molecule(-1) s(-1), and almost exclusively by oxygen-atom abstraction to produce lanthanide-oxide LnO(+) cations. In contrast to results of previous studies with many other molecules, the reaction efficiency exhibits essentially no dependence upon the energy required to promote an electron to achieve a d(1)s(1) excited electronic configuration, in which two non-f electrons are available to Ln(+) for chemical bonding. Apparently the radical character of NO(2) (X (2)A(1)) leads to the efficient formation of LnO(+) by the end-on abstraction of an oxygen atom by Ln(+). In the reactions with La(+), Ce(+), Pr(+) and Gd(+) an additional minor channel (less than 2%) leads to the formation of NO(+). The LnO(+) product ions participate in various secondary and higher order reactions with NO(2) resulting in the formation of ions of the type LnO(x)(NO)(y)(NO(2))(z)(+) with x = 1-2, y = 0-2, and z = 0-2, as well as the ions NO(+) and NO(2)(+).

On the origin of ultrafast nonradiative transitions in nitro-polycyclic aromatic hydrocarbons: Excited-state dynamics in 1-nitronaphthalene

The electronic energy relaxation of 1-nitronaphthalene was studied in nonpolar, aprotic, and protic solvents in the time window from femtoseconds to microseconds. Excitation at 340 or 360 nm populates the Franck-Condon S(1)(pipi( *)) state, which is proposed to bifurcate into two essentially barrierless nonradiative decay channels with sub-200 fs lifetimes. The first main decay channel connects the S(1) state with a receiver T(n) state that has considerable npi( *) character. The receiver T(n) state undergoes internal conversion to populate the vibrationally excited T(1)(pipi( *)) state in 2-4 ps. It is shown that vibrational cooling dynamics in the T(1) state depends on the solvent used, with average lifetimes in the range from 6 to 12 ps. Furthermore, solvation dynamics competes effectively with vibrational cooling in the triplet manifold in primary alcohols. The relaxed T(1) state undergoes intersystem crossing back to the ground state within a few microseconds in N(2)-saturated solutions in all the solvents studied. The second minor channel involves conformational relaxation of the bright S(1) state (primarily rotation of the NO(2)-group) to populate a dissociative singlet state with significant charge-transfer character and negligible oscillator strength. This dissociative channel is proposed to be responsible for the observed photochemistry in 1-nitronaphthalene. Ground- and excited-state calculations at the density functional level of theory that include bulk and explicit solvent effects lend support to the proposed mechanism where the fluorescent S(1) state decays rapidly and irreversibly to dark excited states. A four-state kinetic model is proposed that satisfactorily explains the origin of the nonradiative electronic relaxation pathways in 1-nitronaphthalene.

Thermochemical Properties and Decomposition Pathways of Three Isomeric Semiquinone Radicals

Semiquinones are persistent free environmental radicals formed as important initial products from the decomposition of dihydroxylated benzene isomers. This study develops detailed decomposition pathways for the thermal decomposition of the three isomeric semiquinone radicals. Branching ratios based on the calculated high-pressure limit reaction rate constants predict that p-benzoquinone is a major product from the unimolecular decomposition of the p-semiquinone radical, while the formation of o-benzoquinone from the o-semiquinone radical corresponds to a minor channel. This finding is consistent with the absence of o-benzoquinone from the thermal degradation of the 1,2-dihydroxybenzene isomer and the abundance of p-benzoquinone from the thermal decomposition of 1,4-dihydroxybenzene. Ring contraction/CO elimination is shown to be the dominant sink pathway for the o-semiquinone and m-semiquinone radicals. Thermochemical properties, in terms of enthalpies of formation, entropies, and heat capacities for dihydroxylated benzene isomers, semiquinone radicals, and benzoquinones, are evaluated by quantum chemical calculations. Values of the enthalpies of formation calculated by the B3LYP/GTLarge method show good agreement with those obtained at the G3B3 level of theory.