Decomposition Channels Research Articles

Electron transfer modifies chemical properties of C70 fullerene surface: An ab initio molecular dynamics study of C70O3 molozonides doped with light atoms

Light metal atoms such as Li, K (electronic state 2S1/2) or Ca (1S0) encapsulated in a C70 cage considerably modifies the chemical properties of the fullerene surface due to metal-to-cage electron transfer. H-doped and anion ozonide systems were also considered to validate the electron transfer hypothesis. The relative stabilities of the eight isomers of the C70O3 molozonide series at room temperature depend on the identity of the endohedral guest, as was the preferred channel for thermal decomposition. No electron transfer was observed for the complex N@C70 where the fullerene acts as an inert container for the 4S3/2 radical.

Theoretical investigation on gas-phase reaction of CF3CH2OCH3 with OH radicals and fate of alkoxy radicals (CF3CH(O[rad])OCH3/CF3CH2OCH2O[rad

Detailed theoretical investigation has been performed on the mechanism, kinetics and thermochemistry of the gas phase reactions of CF3CH2OCH3 (HFE-263fb2) with OH radicals using ab-initio and DFT methods. Reaction profiles are modeled including the formation of pre-reactive and post-reactive complexes at entrance and exit channels, respectively. Our calculations reveal that hydrogen abstraction from the CH2 group is thermodynamically and kinetically more facile than that from the CH3 group. Using group-balanced isodesmic reactions, the standard enthalpies of formation for CF3CH2OCH3 and radicals (CF3CHOCH3 and CF3CH2OCH2) are also reported for the first time. The calculated bond dissociation energies for the CH bonds are in good agreement with experimental results. At 298K, the calculated total rate coefficient for CF3CH2OCH3+OH reactions is found to be in good agreement with the experimental results. The atmospheric fate of the alkoxy radicals, CF3CH(O)OCH3 and CF3CH2OCH2O are also investigated for the first time using the same level of theory. Out of three plausible decomposition channels, our results clearly point out that reaction with O2 is not the dominant path leading to the formation of CF3C(O)OCH3 for the decomposition of CF3CH(O)OCH3 radical in the atmosphere. This is in accord with the recent report of Osterstrom et al. [CPL 524 (2012) 32] but found to be in contradiction with experimental finding of Oyaro et al. [JPCA 109 (2005) 337].

Theoretical study on the selectivity of the insertion xenon atom into hypohalous acids

The structures, harmonic/anharmonic vibrational frequencies, stabilities and bondings of HOXeX/HXeOX (X=F, Cl, Br and I) were investigated. Both HXeOX/HOXeX were confirmed to be stable, and HOXeX is more stable thermodynamically than corresponding HXeOX. The two-body decomposition reactions of them are exothermic, while the three-body ones are endothermic. However, both of them are stabilized kinetically with respect to the two-/three-body decomposition reactions by enough highly energy barriers. The three-body reactions are predicted to be the mainly decomposition channels because of the lower energy barriers of TS2. The VSCF analysis shows that the H–Xe (HXeOX) and O–H (HOXeX) stretching modes are highly anharmonic and are very likely to be observed experimentally. The nature of the bondings in HXeOX/HOXeX were analyzed by QTAIM, LMO-EDA and Löwdin/NPA population methods, and found that the electrostatic interaction is the main driving force for the formation of ionic (HXe)+(OX)− or (HO)+(XeX)−.

Secondary channels in the thermal decomposition of monomethylhydrazine (CH3NHNH2)

The possible role of molecular decomposition channels in MMH is explored through additional investigations on triplet channels, roaming radical channels, and previously unexplored pathways on the potential energy surface.

Theoretical investigation on the atmospheric fate of the CF3C(O)OCH(O)CF3 radical: alpha-ester rearrangement vs. oxidation

A detailed quantum chemical study is performed on the unimolecular decomposition reaction of the alkoxy radical, CF3C(O)OCH(O)CF3 produced from CF3C(O)OCH2CF3, trifluoroethyl trofluoroacetate (TFETFA) at the MPWB1K and M06-2X level of theories using the 6-31+G(d,p) basis set. Five plausible decomposition pathways including reaction with O2, α-ester rearrangement and thermal decomposition (C–C, C–H and C–O bonds scission) have been considered in detail. Out of the five prominent decomposition channels, our results reveal that reaction with O2 is the dominant path for the decomposition of the CF3C(O)OCH(O)CF3 radical in the atmosphere involving the lowest energy barrier which is in accordance with recent experimental findings. Our theoretical results also suggest that α-ester rearrangement leading to the formation of trifluoroacetic acid (TFA) has a negligible contribution for decomposition of the title alkoxy radical. The thermal rate constants for the above decomposition pathways are evaluated using Canonical Transition State Theory (CTST) at 298 K.

Theoretical investigation of atmospheric chemistry of volatile anaesthetic sevoflurane: reactions with the OH radicals and atmospheric fate of the alkoxy radical (CF3)2CHOCHFO: thermal decomposition vs. oxidation

Reaction profile (kcal mol−1) for (CF3)2CHOCHFO radical at the M06-2X/6-311++G(d,p) level.

Thermal decomposition products of butyraldehyde

The thermal decomposition of gas-phase butyraldehyde, CH3CH2CH2CHO, was studied in the 1300-1600 K range with a hyperthermal nozzle. Products were identified via matrix-isolation Fourier transform infrared spectroscopy and photoionization mass spectrometry in separate experiments. There are at least six major initial reactions contributing to the decomposition of butyraldehyde: a radical decomposition channel leading to propyl radical + CO + H; molecular elimination to form H2 + ethylketene; a keto-enol tautomerism followed by elimination of H2O producing 1-butyne; an intramolecular hydrogen shift and elimination producing vinyl alcohol and ethylene, a β-C-C bond scission yielding ethyl and vinoxy radicals; and a γ-C-C bond scission yielding methyl and CH2CH2CHO radicals. The first three reactions are analogous to those observed in the thermal decomposition of acetaldehyde, but the latter three reactions are made possible by the longer alkyl chain structure of butyraldehyde. The products identified following thermal decomposition of butyraldehyde are CO, HCO, CH3CH2CH2, CH3CH2CH=C=O, H2O, CH3CH2C≡CH, CH2CH2, CH2=CHOH, CH2CHO, CH3, HC≡CH, CH2CCH, CH3C≡CH, CH3CH=CH2, H2C=C=O, CH3CH2CH3, CH2=CHCHO, C4H2, C4H4, and C4H8. The first ten products listed are direct products of the six reactions listed above. The remaining products can be attributed to further decomposition reactions or bimolecular reactions in the nozzle.

Research of Improved Algorithm for MIMO Channel Estimation

We introduced an improved singular value decomposition (SVD) channel estimation algorithm for multiple-input multiple-output (MIMO) wireless communication system. The algorithm is supposed to solve the issue that the channel estimation result is not accurate when the training sequences have some 0 elements. The improvement is also applicable in the other channel estimation algorithms. We made some comparisons between the linear least squares (LS) and the linear minimum mean square error (LMMSE) channel estimation, the traditional singular value decomposition and the improved SVD algorithm to demonstrate the efficiency. Results show that the proposed improved SVD algorithm has better performance in mean square error (MSE) and bit error rate (BER) of channel estimation and the estimated values approach the actual channel state.

Photolysis of Dimethylcarbamoyl Azide in an Argon Matrix: Spectroscopic Identification of Dimethylamino Isocyanate and 1,1-Dimethyldiazene

The UV photolysis of dimethylcarbamoyl azide has been investigated in an argon matrix at cryogenic temperatures. The products of the photolysis were identified by infrared spectroscopy supported by quantum-chemical calculations. Sequential formation of dimethylamino isocyanate (Me2N-NCO), 1,1-dimethyldiazene (Me2N═N), and ethane was established. Therefore, the major decomposition channel is identified as Me2NC(O)N3 → Me2N-NCO → Me2N═N → Me-Me, via consecutive N2, CO, and N2 eliminations. Ground-state geometries, vibrational frequencies, IR intensities, and UV excitation energies of the transient dimethylamino isocyanate and 1,1-dimethyldiazene have been computed using the B3LYP and SAC-CI methods and the aug-cc-pVTZ basis set.

Ab Initio Chemical Kinetics for SiH2 + Si2H6 and SiH3 + Si2H5 Reactions and the Related Unimolecular Decomposition of Si3H8 under a-Si/H CVD Conditions

The kinetics and mechanisms for SiH2 + Si2H6 and SiH3 + Si2H5 reactions and the related unimolecular decomposition of Si3H8 have been investigated by ab initio molecular orbital theory based on the QCISD(T)/CBS//QCISD/6-311++G(d,p) method in conjunction with quantum statistical variational Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. For the barrierless radical association processes, their variational transition states have been characterized by the CASPT2//CASSCF method. The species involved in the study are known to coexist under CVD conditions. The results show that the association reaction of SiH2 and Si2H6 producing Si3H8 occurs by insertion via its lowest-energy path forming a loose hydrogen-bonding molecular complex with 8.3 kcal/mol binding energy; the reaction is exothermic by 55.0 kcal/mol. The chemically activated Si3H8 adduct can fragment by several paths, producing SiH4 + SiH3SiH (-0.7 kcal/mol), Si(SiH3)2 + H2 (-1.4 kcal/mol), and SiH3SiH2SiH + H2 (-1.4 kcal/mol). The predicted enthalpy changes as given agree well with available thermochemical data. Three other decomposition channels of Si3H8 occurring by Si-H or Si-Si breaking were found to be highly endothermic, and the reactions take place without a well-defined barrier. The heats of formation of Si3H8, SiH2SiH, Si2H4, i-Si3H7, n-Si3H7, Si(SiH3)2, and SiH3SiH2SiH have been predicted and found to be in close agreement with those available data in the literature. The product branching rate constants for SiH2 + Si2H6 and SiH3 + Si2H5 reactions and the thermal unimolecular decomposition of Si3H8 for all low-energy paths have been calculated with multichannel variational RRKM theory covering varying P,T conditions typically employed in PECVD and Cat-CVD processes for hydrogenated amorphous silicon (a-Si/H) film growth. The results were also found to be in good agreement with available kinetic data. Our kinetic results may be employed to model and control very large-area a-Si/H film growth for a new generation of solar cell applications.

Decomposition Pathways of the Neutral and Protonated Formamide in Some Lower-Lying Excited States

Unimolecular decompositions of neutral (NH2CHO) and protonated (NH3CHO(+)) formamide, an active precursor of biomolecules in prebiotic chemistry, are investigated in the ground (S0) and first triplet (T1) and singlet (S1) excited states. Different decomposition channels including the homolytic bond dissociations, dehydration, decarbonylation, dehydrogenation, etc., are explored using coupled-cluster theory (CCSD(T)/CBS method) for both S0 and T1 states and RASPT2(18,15)/6-31G(d,p) computations for the S1 state. On S1 and T1 energy surfaces, formamide preferentially follows C-N homolytic bond cleavages forming NH2 + HCO radical pairs. Formation of HCN and HNC from dehydration of neutral and protonated formamide via formimic acid and aminohydroxymethylene isomers has higher energy barriers. A strong stabilization upon triplet excitation of the two latter isomers significantly facilitates the interconversions between isomers, and thus considerably reduces the energy barriers for dehydration pathways. The most probable pathways for HCN and HNC generation are found to be dehydration of formamide in the T1 state. Dehydration pathways from the neutral S1 and protonated T1 forms lead to stable complexes of HCN and HNC with water but are associated with large energy barriers. Overall, in the lower-lying excited states of either neutral or protonated formamide, dehydration is not competitive with homolytic C-N bond cleavages, which finally lead to formation of CO.

Shock tube study of methanol, methyl formate pyrolysis: CH3OH and CO time-history measurements

Methanol and methyl formate pyrolysis were studied by measuring CH3OH and CO concentration time-histories behind reflected shock waves. In the study of methanol pyrolysis, experimental conditions covered temperatures of 1266–1707K, pressures of 1.1–2.5atm, and initial fuel concentrations of 1% and 0.2% with argon as the bath gas. Detailed comparisons of CH3OH and CO concentration profiles with the predictions of the detailed kinetic mechanism of Li et al. (2007) [8] were made. Such comparisons combined with sensitivity analysis identified the need to include an additional methanol decomposition channel, CH3OH↔CH2(S)+H2O, into the mechanism. Pathway and sensitivity analyses for methanol decomposition were performed, leading to rate constant recommendations both for CH3OH unimolecular decomposition and H-abstraction reactions with improved model performance. In the study of methyl formate pyrolysis, methanol concentration time-histories were measured at temperatures over the range of 1261–1524K, pressures near 1.5atm, and initial fuel concentrations of 1% with argon as the bath gas. Our current work, and CO time-histories from previous work, indicates that the Dooley et al. (2010) [3] model is able to accurately simulate most species concentrations in shock tube experiments at early times. However, model improvement is still needed to match the CH3OH and CO time-histories at later times. Incorporation of the modified rate constants in the methanol sub-mechanism leads to good predictions of the full methanol time-histories at all temperatures. The kinetic implications of some aspects of the CO time-histories and suggestions for further improving the predictive capabilities of these mechanisms are discussed. The current results are the first quantitative measurements of CH3OH time-histories in shock tube experiments, and hence are a critical step toward understanding of the chemical kinetics of oxygenates.

Association reaction between SiH3 and H2O2: a computational study of the reaction mechanism and kinetics

The association reaction between silyl radical (SiH3) and H2O2 has been studied in detail using high-level composite ab initio CBS-QB3 and G4MP2 methods. The global hybrid meta-GGA M06 and M06-2X density functionals in conjunction with 6-311++G(d,p) basis set have also been applied. To understand the kinetics, variational transition-state theory calculation is performed on the first association step, and successive unimolecular reactions are subjected to Rice–Ramsperger–Kassel–Marcus calculations to predict the reaction rate constants and product branching ratios. The bimolecular rate constant for SiH3–H2O2 association in the temperature range 250–600 K, k(T) = 6.89 × 10−13 T −0.163exp(−0.22/RT) cm3 molecule−1 s−1 agrees well with the current literature. The OH production channel, which was experimentally found to be a minor one, is confirmed by the rate constants and branching ratios. Also, the correlation between our theoretical work and experimental literature is established. The production of SiO via secondary reactions is calculated to be one of the major reaction channels from highly stabilized adducts. The H-loss pathway, i.e., SiH2(OH)2 + H, is the major decomposition channel followed by secondary dissociation leading to SiO.

Shock Tube Measurements of the tert-Butanol + OH Reaction Rate and the tert-C4H8OH Radical β-Scission Branching Ratio Using Isotopic Labeling

The overall rate constant for the reaction tert-butanol + OH → products was determined experimentally behind reflected shock waves by using (18)O-substituted tert-butanol (tert-butan(18)ol) and tert-butyl hydroperoxide (TBHP) as a fast source of (16)OH. The data were acquired from 900 to 1200 K near 1.1 atm and are best fit by the Arrhenius expression 1.24 × 10(-10) exp(-2501/T [K]) cm(3) molecule(-1) s(-1). The products of the title reaction include the tert-C4H8OH radical that is known to have two major β-scission decomposition channels, one of which produces OH radicals. Experiments with the isotopically labeled tert-butan(18)ol also lead to an experimental determination of the branching ratio for the β-scission pathways of the tert-C4H8OH radical by comparing the measured pseudo-first-order decay rate of (16)OH in the presence of excess tert-butan(16)ol with the respective decay rate of (16)OH in the presence of excess tert-butan(18)ol. The two decay rates of (16)OH as a result of reactions with the two forms of tert-butanol differ by approximately a factor of 5 due to the absence of (16)OH-producing pathways in experiments with tert-butan(18)ol. This indicates that 80% of the (16)OH molecules that react with tert-butan(16)ol will reproduce another (16)OH molecule through β-scission of the resulting tert-C4H8(16)OH radical. (16)OH mole fraction time histories were measured using narrow-line-width laser absorption near 307 nm. Measurements were performed at the line center of the R22(5.5) transition in the A-X(0,0) band of (16)OH, a transition that does not overlap with any absorption features of (18)OH, hence yielding a measurement of (16)OH mole fraction that is insensitive to any production of (18)OH.

Theoretical study of elementary reactions of dehydrogenation of magnesium, calcium, zinc, and beryllium amminoborate and amminoalanate complexes

The potential energy surfaces along minimal-energy pathways for elementary reactions of hydrogen molecule elimination from the complex molecules of amminoborates and amminoalanates M(LH4)2(NH3) and M(LH4)2(NH3)2 and the [M(LH4)2(NH3)2]2 dimers (M = Be, Mg, Ca, or Zn; L = B or Al) have been calculated by the density functional theory B3LYP method. The equilibrium structures and normal mode frequencies for local minima and transition states corresponding to these molecules and their fragmentation products have been determined. The energies and activation barriers of different decomposition channels have been estimated. It has been demonstrated that the introduction of an ammonia molecule into the coordination sphere of magnesium reduces the barrier to dehydrogenation of ammine complexes as compared with the M(BH4)2 borates and M(AlH4)2 alanates. The barriers for the amminoalanates are lower than those for the amminoborates; however, the former are no lower than ∼30 kcal/mol and hinder the dehydrogenation of ammine complexes at the level of isolated molecules. Going from the M(LH4)2(NH3)2 monomers to the [M(LH4)2(NH3)2]2 dimers has little effect on the barriers. The trends in the behavior of the molecular characteristics of the complexes as we move down Group II of the Periodic table are considered.

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.

Vacuum Ultraviolet Photoionization and Dissociative Photoionization of Capecitabine, 5′-Deoxy-5-Fluorocytidine, and 5′-Deoxy-5-Fluorouridine

Vacuum ultraviolet (VUV) photoionization and dissociative photoionization of capecitabine and its metabolites, 5′-deoxy-5-fiuorocytidine (5′-DFCR) and 5′-deoxy-5- fluorouridine (5′-DFUR), were investigated with infrared laser desorption/tunable synchrotron VUV photoionization mass spectrometry. Molecular ions (M+) with small amounts of fragments can be found for these compounds at relatively low photon energies, while more fragment ions would be produced by increasing the photon energies. (M−H2O)+, (base+H)+, (base+2H)+, (base+30)+, (base+60)+, and sugar moiety were proposed for these nucleoside drugs with similar backbones. Decomposition channels for the major fragments were discussed in detail. Moreover, ab initio calculations were introduced to study the dehydration pathways of three fluoro-nucleosides. Corresponding appearance energies for the (M−H2O)+ ions were computed.

Tunable-Q contourlet transform for image representation

A novel tunable-quality-factor (tunable-Q) contourlet transform for geometric image representation is proposed. The Laplacian pyramid in original contourlet decomposes a signal into channels that have the same bandwidth on a logarithmic scale, and is not suitable for images with different behavior in frequency domain. We employ a new tunable-Q decomposition defined in the frequency domain by which one can flexibly tune the bandwidth of decomposition channels. With an acceptable redundancy, this tunable-Q contourlet is also anti-aliasing and its basis is sharply localized in the desired area of frequency and spatial domain. Our experiments in nonlinear approximation and denoising show that the contourlet using a better-suitable quality factor can achieve a more promising performance and often outperform wavelets and the previous contourlets both in visual quality and in terms of peak signal-to-noise ratio.

Theoretical studies on the unimolecular decomposition of nitroglycerin

To improve the understanding of the unimolecular decomposition mechanism of nitroglycerin (NG) in the gas phase, density functional theory calculations were performed to determine various decomposition channels at the B3LYP/6-311G** level. For the unimolecular decomposition mechanism of NG, we find two main mechanisms: (I) homolytic cleavage of O-NO2 to form •NO2 and CH2ONO2CHONO2CH2O•, which subsequently decomposes to form •CHO, •NO2, and 2CH2O; (II) successive HONO eliminations to form HONO and CHO-CO-CHO, which subsequently decomposes to form CH2O + 2CO2 and •CHO + CO. We also find that the former channel has slightly smaller activation energy than the latter one. In addition, the rate constants of the initial process of the two decomposition channels were calculated. The results show that the O-NO2 cleavage pathway occurs more easily than the HONO elimination.

Unimolecular decomposition of 2,5-dimethylfuran: a theoretical chemical kinetic study

The unimolecular decomposition of 2,5-dimethylfuran (DMF), a promising next-generation biofuel, was studied at the CBS-QB3 level of theory. As most of its decomposition routes remain unknown, a large number of pathways were explored: initial C-H bond fission, biradical ring opening, H-atom and CH(3)-group transfers involving carbene intermediates. Based on the computed potential energy surfaces, thermochemical data and high-pressure limit rate constants were determined and included in a small detailed kinetic mechanism for DMF unimolecular decomposition. Simulations performed under the conditions of recent experimental data focusing on the initial steps in DMF thermal decomposition showed that the unimolecular decomposition of DMF is dominated by two product channels. For typical combustion conditions, the major product channel (~70% at 1500 K and 1 bar) is reached by a 3,2-hydrogen transfer in DMF leading to a carbene intermediate that rearranges to hexa-3,4-dien-2-one which in turn decomposes into CH(3)CO and C(4)H(5) by initial C-C bond fission. In contrast with previous studies, the initial C-H bond fission in DMF has not been found to be the major decomposition channel (~30% at 1500 K and 1 bar). Pressure effects were probed using a semi-quantitative approach and were found to be negligible above 1 bar. Below atmospheric pressure, initial C-H bond cleavage yields increase while CH(3)CO + C(4)H(5) branching ratios decrease. This study brings a new understanding of the nature of the initial radicals and molecules created upon thermal activation of DMF.