共查询到20条相似文献,搜索用时 46 毫秒
1.
Troya D Schatz GC Garton DJ Brunsvold AL Minton TK 《The Journal of chemical physics》2004,120(2):731-739
The excitation function for the reaction, O(3P)+CH4-->H+OCH3, has been measured in a crossed molecular beams experiment and determined with direct dynamics calculations that use the quasiclassical trajectory method in conjunction with a recently developed semiempirical Hamiltonian. Good agreement is found between experiment and theory, enabling us to address two fundamental issues for the O(3P)+CH4 reaction that arise for all O(3P)+saturated hydrocarbon reactions: (1) the importance of triplet excited states that correlate adiabatically to ground-state reactants and products and (2) the importance of intersystem crossing processes involving the lowest singlet surface [corresponding to reaction with O(1D)]. Our results indicate that the first excited triplet surface contributes substantially to the cross section when the collision energy exceeds the reaction barrier (approximately 2 eV) by more than 0.5 eV. Although triplet-singlet crossings may occur at all energies, we have found that their effect on the excitation function is negligible for the collision energies studied-up to 1.5 eV above threshold. 相似文献
2.
The C(2)H + O((3)P) --> CH(A) + CO reaction is investigated using Fourier transform visible emission spectroscopy. The O((3)P) and C(2)H radicals are produced by simultaneous 193 nm photolysis of SO(2) and C(2)H(2) precursors, respectively. The nascent vibrational and rotational distributions of the CH(A) product are obtained under time-resolved, but quasi-steady-state, conditions facilitated by the short lifetime of the CH(A) emission. The vibrational temperature of the CH(A) product is found to be appreciably hotter (2800 +/- 100 K) than the rotational distributions in the v' = 0 (1400 +/- 100 K) and v' = 1 (1250 +/- 250 K) levels. The results suggest that the reaction may proceed through an electronically excited HCCO() intermediate; moreover, the vibrational excitation compared to rotational excitation is higher than expected based on a statistical distribution of energy and may be the result of geometrical changes in the transition state. The CH(A) emission is also observed in a C(2)H(2)/O/H reaction mixture using a microwave discharge apparatus to form O atoms, with subsequent H atom production. The nascent rotational and vibrational distributions of the CH(A) determined by the microwave discharge apparatus are very similar to the CH(A) distributions obtained in the photodissociation experiment. The results support the idea that the C(2)H + O((3)P) reaction may play a role in low-pressure C(2)H(2)/O/H flames, as previously concluded. 相似文献
3.
The O((1)D) + C(3)H(8) reaction has been reinvestigated using the universal crossed molecular beam method. Three reaction channels, CH(3) + C(2)H(4)OH, C(2)H(5) + CH(2)OH, and OH + C(3)H(7), have been observed. All three channels are significant in the title reaction with the C(2)H(5) formation process to be the most important, while the CH(3) formation and the OH formation channels are about equal. Product kinetic energy distributions and angular distributions have been determined for the three reaction channels observed. The oxygen-containing radicals in the CH(3) and C(2)H(5) formation pathways show forward-backward symmetric angular distribution relative to the O atom beam, while the OH product shows a clearly forward angular distribution. These results indicate that the OH formation channel seems to exhibit different dynamics from the CH(3) and C(2)H(5) channels. 相似文献
4.
The reactions of ground state Y (a(2)D) with H(2)CO and CH(3)CHO were studied at a range of collision energies in crossed molecular beams. For reaction with H(2)CO, three product channels were observed: formation of YH(2) + CO, YCO + H(2), and YHCO + H. Reaction with CH(3)CHO led to three analogous product channels involving formation of HYCH(3) + CO, YCH(2)CO + H(2), and YCH(3)CO + H. The calculated CCSD(T) energetics and DFT geometries for key intermediates in both reactions, together with RRKM theory, are used to calculate a priori the branching ratios between various product channels. These calculated values are compared to those obtained experimentally. 相似文献
5.
The reactions between OH+(3Sigma-) and C2H2 have been studied using crossed ion and molecular beams and density functional theory calculations. Both charge transfer and proton transfer channels are observed. Products formed by carbon-carbon bond cleavage analogous to those formed in the isoelectronic O(3P)+C2H2 reaction, e.g., 3CH2 + HCO+, are not observed. The center of mass flux distributions of both product ions at three different energies are highly asymmetric, with maxima close to the velocity and direction of the precursor acetylene beam, characteristic of direct reactions. The internal energy distributions of the charge transfer products are independent of collision energy and are peaked at the reaction exothermicity, inconsistent with either the existence of favorable Franck-Condon factors or energy resonance. In proton transfer, almost the entire reaction exothermicity is transformed into product internal excitation, consistent with mixed energy release in which the proton is transferred with both the breaking and forming bonds extended. Most of the incremental translational energy in the two higher-energy experiments appears in product translational energy, providing an example of induced repulsive energy release. 相似文献
6.
The reactions between phenyl radicals (C6H5) and propylene (CH3CHCH2) together with its D6- and two D3-isotopologues were studied under single collision conditions using the crossed molecular beams technique. The chemical dynamics inferred from the center-of-mass translational and angular distributions suggests that the reactions are indirect and initiated by an addition of the phenyl radical to the alpha-carbon atom (C1 carbon atom) of the propylene molecule at the =CH2 unit to form a radical intermediate (CH3CHCH2C6H5) on the doublet surface. Investigations with D6-propylene specified that only a deuterium atom was emitted; the phenyl group was found to stay intact. Studies with 1,1,2-D3- and 3,3,3-D3-propylene indicated that the initial collision complexes CH3CDCD2C6H5 (from 1,1,2-D3-propylene) and CD3CHCH2C6H5 (from 3,3,3-D3-propylene) eject both a hydrogen atom via rather loose exit transition states to form the D3-isotopomers of cis/trans-1-phenylpropene (CH3CHCHC6H5) (80-90%) and 3-phenylpropene (H2CCHCH2C6H5) (10-20%), respectively. Implications of these findings for the formation of polycyclic aromatic hydrocarbons (PAHs) and their precursors in combustion flames are discussed. 相似文献
7.
Casavecchia P Capozza G Segoloni E Leonori F Balucani N Volpi GG 《The journal of physical chemistry. A》2005,109(16):3527-3530
The crossed molecular beam scattering technique with soft electron ionization (EI) is used to disentangle the complex dynamics of the polyatomic O(3P) + C2H4 reaction, which is of great relevance in combustion and atmospheric chemistry. Exploiting the newly developed capability of attaining universal product detection by using soft EI, at a collision energy of 54.0 kJ mol(-1), five different primary products have been identified, which correspond to the five exoergic competing channels leading to CH2CHO(vinoxy) + H, CH3CO(acetyl) + H, CH3(methyl) + HCO(formyl), CH2(methylene) + HCHO(formaldehyde), and CH2CO(ketene) + H2. From laboratory product angular and velocity distributions, center-of-mass product angular and translational energy distributions and the relative branching ratios for each channel have been obtained, affording an unprecedented characterization of this important reaction. 相似文献
8.
The potential energy surfaces of the two lowest-lying triplet electronic surfaces 3A' and 3A' for the O(3P) + C2H2 reaction were theoretically reinvestigated, using various quantum chemical methods including CCSD(T), QCISD, CBS-QCI/APNO, CBS-QB3, G2M(CC,MP2), DFT-B3LYP and CASSCF. An efficient reaction pathway on the electronically excited 3A' surface resulting in H(2S) + HCCO(A2A') was newly identified and is predicted to play an important role at higher temperatures. The primary product distribution for the multistate multiwell reaction was then determined by RRKM statistical rate theory and weak-collision master equation analysis using the exact stochastic simulation method. Allowing for nonstatistical behavior of the internal rotation mode of the initial 3A' adducts, our computed primary-product distributions agree well with the available experimental results, i.e., ca. 80% H(2S) + HCCO(X2A' + A2A') and 20% CH2(X3B1) + CO(X1sigma+) independent of temperature and pressure over the wide 300-2000 K and 0-10 atm ranges. The thermal rate coefficient k(O + C2H2) at 200-2000 K was computed using multistate transition state theory: k(T) = 6.14 x 10(-15)T (1.28) exp(-1244 K/T) cm3 molecule(-1) s(-1); this expression, obtained after reducing the CBS-QCI/APNO ab initio entrance barriers by 0.5 kcal/mol, quasi-perfectly matches the experimental k(T) data over the entire 200-2000 K range, spanning 3 orders of magnitude. 相似文献
9.
Leonori F Petrucci R Segoloni E Bergeat A Hickson KM Balucani N Casavecchia P 《The journal of physical chemistry. A》2008,112(7):1363-1379
A detailed investigation of the dynamics of the reactions of ground- and excited-state carbon atoms, C(3P) and C(1D), with acetylene is reported over a wide collision energy range (3.6-49.1 kJ mol-1) using the crossed molecular beam (CMB) scattering technique with electron ionization mass spectrometric detection and time-of-flight (TOF) analysis. We have exploited the capability of (a) generating continuous intense supersonic beams of C(3P, 1D), (b) crossing the two reactant beams at different intersection angles (45, 90, and 135 degrees ) to attain a wide range of collision energies, and (c) tuning the energy of the ionizing electrons to low values (soft ionization) to suppress interferences from dissociative ionization processes. From angular and TOF distribution measurements of products at m/z=37 and 36, the primary reaction products of the C(3P) and C(1D) reactions with C2H2 have been identified to be cyclic (c)-C3H + H, linear (l)-C3H + H, and C3 + H2. From the data analysis, product angular and translational energy distributions in the center-of-mass (CM) system for both the linear and cyclic C3H isomers as well as the C3 product from C(3P) and for l/c-C3H and C3 from C(1D) have been derived as a function of collision energy from 3.6 to 49.1 kJ mol-1. The cyclic/linear C3H ratio and the C3/(C3 + c/l-C3H) branching ratios for the C(3P) reaction have been determined as a function of collision energy. The present findings have been compared with those from previous CMB studies using pulsed beams; here, a marked contrast is noted in the CM angular distributions for both C3H- and C3-forming channels from C(3P) and their trend with collision energy. Consequently, the interpretation of the reaction dynamics derived in the present work contradicts that previously proposed from the pulsed CMB studies. The results have been discussed in the light of the available theoretical information on the relevant triplet and singlet C3H2 ab initio potential energy surfaces (PESs). In particular, the branching ratios for the C(3P) + C2H2 reaction have been compared with the available theoretical predictions (approximate quantum scattering calculations and quasiclassical trajectory calculations on ab initio triplet PESs and, very recent, statistical calculations on ab initio triplet PESs as well as on ab initio triplet/singlet PESs including nonadiabatic effects, that is, intersystem crossing). While the experimental branching ratios have been corroborated by the statistical predictions, strong disagreement has been found with the results of the dynamical calculations. The astrophysical implications of the present results have been noted. 相似文献
10.
We investigated the title reaction at collision energy 3.5 kcal mol(-1) in a crossed molecular beam apparatus using undulator radiation as an ionization source. Time-of-flight (TOF) spectra of product C(3)H(3) were measured in laboratory angles from 20° to 100° using two photoionization energies 9.5 and 11.6 eV. These two sets of experimental data exhibit almost the same TOF distributions and laboratory angular distributions. From the best simulation, seven angle-specific kinetic-energy distributions and a nearly isotropic angular distribution are derived for product channel C(3)H(3) + H that has an average kinetic-energy release of 15.5 kcal mol(-1), corresponding to an average internal energy of 33.3 kcal mol(-1) in C(3)H(3). Furthermore, TOF spectra of product C(3)H(3) were measured at laboratory angle 52° with ionizing photon energies from 7 to 12 eV. The appearance of TOF spectra remains almost the same, indicating that a species exclusively contributes to product C(3)H(3); the species is identified as H(2)CCCH (propargyl) based on the ionization energy of 8.6 ± 0.2 eV and the maximal kinetic-energy release of 49 kcal mol(-1). Theoretical calculations indicate that the rapid inversion mechanism and rotation in intermediate H(2)CCCH(2) can result in a forward-backward symmetric angular distribution for product C(3)H(3) + H. The present work avoids the interference of reactions of C((1)D) and C(2) radicals with C(2)H(4) and rules out the probability of production of other isomers like c-C(3)H(3) and H(3)CCC proposed in the previous work at least at the investigated collision energy. 相似文献
11.
In an electron impact dissociative ionization experiment on C(2)H(5)OH, the formation of molecular ions requiring rearrangement of H atoms has been studied using a momentum spectrometer. H(3) (+), H(2) (+), HOH(+), and H(2)OH(+) observed in the experiment are molecular ions of this type. By comparing the mass spectrum of C(2)H(5)OH with that of its isotopomer C(2)H(5)OD, we determine the proportions of H-bond rearrangements involving carbon and oxygen sites. We find that the formation of H(3) (+) due to the breaking of the O-H bond and rearrangement of the H atoms on the CH(2) site is about 2.5 times as likely as its formation involving atoms from the CH(3) site alone. No such difference is seen in case of the H(2) (+) ion. The role of the O-H bond in formation of all observed ions has been assessed. Kinetic energy distributions of the molecular ions suggest that two or three electronically excited states contribute to their formation. 相似文献
12.
The reaction C(2)H + O(2) --> CH(A(2)Delta) + CO(2) is investigated using Fourier transform visible emission spectroscopy. C(2)H radicals, produced by 193 nm photolysis of C(2)H(2), react with O(2) molecules at low total pressures to produce electronically excited CH(A(2)Delta). Observation of the CH(A(2)Delta-X(2)Pi) electronic emission to infer nascent rotational and vibrational CH(A(2)Delta) distributions provides information about energy partitioning in the CH(A(2)Delta) fragment during the reaction. The rotational and vibrational populations of the CH(A(2)Delta) product are determined by fitting the rotationally resolved experimental spectra with simulated spectra. The CH(A(2)Delta) product is found to be rotationally and vibrationally excited with T(rot) congruent with 1150 K and T(vib) congruent with 1900 K. The mechanism for this reaction proceeds through one of two five-atom intermediates and requires a crossing between electronic potential surfaces. The rotational excitation suggests a bent geometry for the final intermediate of this reaction before dissociation to products, and the vibrational excitation involves an elongation of the C-H bond from the compressed transition state to the final CH(A) state. 相似文献
13.
Casavecchia P Balucani N Cartechini L Capozza G Bergeat A Volpi GG 《Faraday discussions》2001,(119):27-49; discussion 121-43
The dynamics of some elementary reactions of N(2D), C(3P,1D) and CN(X2 sigma +) of importance in combustion have been investigated by using the crossed molecular beam scattering method with mass spectrometric detection. The novel capability of producing intense, continuous beams of the radical reagents by a radio-frequency discharge beam source was exploited. From angular and velocity distribution measurements obtained in the laboratory frame, primary reaction products have been identified and their angular and translational energy distributions in the center-of-mass system, as well as branching ratios, have been derived. The dominant N/H exchange channel has been examined in the reaction N(2D) + CH4, which is found to lead to H + CH2NH (methylenimine) and H + CH3N (methylnitrene); no H2 elimination is observed. In the reaction N(2D) + H2O the N/H exchange channel has been found to occur via two competing pathways leading to HNO + H and HON + H, while formation of NO + H2 is negligible. Formation of H + H2CCCH (propargyl) is the dominant pathway, at low collision energy (Ec), of the C(3P) + C2H4 reaction, while at high Ec formation of the less stable C3H3 isomers (cyclopropenyl and/or propyn-1-yl) also occurs; the H2 elimination channel is negligible. The H elimination channel has also been found to be the dominant pathway in the C(3P,1D) + CH3CCH reaction leading to C4H3 isomers and, again, no H2 elimination has been observed to occur. In contrast, both H and H2 elimination, leading in comparable ratio to C3H + H and C3(X1 sigma g+) + H2(X1 sigma g+), respectively, have been observed in the reaction C(3P) + C2H2(X1 sigma g+). The occurrence of the spin-forbidden molecular pathway in this reaction, never detected before, has been rationalized by invoking the occurrence of intersystem crossing between triplet and singlet manifolds of the C3H2 potential energy surfaces. The reaction CN(X2 sigma +) + C2H2 has been found to lead to internally excited HCCCN (cyanoacetylene) + H. For all the reactions the dynamics have been discussed in the light of recent theoretical calculations on the relevant potential energy surfaces. Previous, lower resolution studies on C and CN reactions carried out using pulsed beams are noted. Finally, throughout the paper the relevance of these results to combustion chemistry is considered. 相似文献
14.
Chemical dynamics of the formation of the 1,3-butadiynyl radical (C4H(X2Sigma+)) and its isotopomers
The reaction of dicarbon molecules in their electronic ground, C2(X1Sigma(g)+), and first excited state, C2(a3Pi(u)), with acetylene, C2H2(X1Sigma(g)+), to synthesize the 1,3-butadiynyl radical, C4H(X2Sigma+), plus a hydrogen atom was investigated at six different collision energies between 10.6 and 47.5 kJ mol(-1) under single collision conditions. These studies were contemplated by crossed molecular beam experiments of dicarbon with three acetylene isotopomers C2D2(X1Sigma(g)+), C2HD (X1Sigma+), and 13C2H2(X1Sigma(g)+) to elucidate the role of intersystem crossing (ISC) and of the symmetry of the reaction intermediate(s) on the center-of-mass functions. On the singlet surface, dicarbon was found to react with acetylene through an indirect reaction mechanism involving a diacetylene intermediate. The latter fragmented via a loose exit transition state via an emission of a hydrogen atom to form the 1,3-butadiynyl radical C4H(X2Sigma+). The D(infinity)(h) symmetry of the decomposing diacetylene intermediate results in collision-energy invariant, isotropic (flat) center-of-mass angular distributions of this microchannel. Isotopic substitution experiments suggested that at least at a collision energy of 29 kJ mol(-1), the diacetylene isotopomers are long-lived with respect to their rotational periods. On the triplet surface, the reaction involved three feasible addition complexes located in shallower potential energy wells as compared to singlet diacetylene. The involvement of the triplet surface accounted for the asymmetry of the center-of-mass angular distributions. The detection of the 1,3-butadiynyl radical, C4H(X2Sigma+), in the crossed beam reaction of dicarbon molecules with acetylene presents compelling evidence that the 1,3-butadiynyl radical can be formed via bimolecular reactions involving carbon clusters in extreme environments such as circumstellar envelopes of dying carbon stars and combustion flames. 相似文献
15.
A concerted three-body formation X+Y+C2H4 in the photodissociation of CH2XCH2Y (X,Y=Br,Cl) at 193 nm
The photodissociation of CH2XCH2Y (X,Y=Br,Cl) through absorption of 193 nm photons was investigated using product translational spectroscopy. No stable CH2BrCH2 or CH2ClCH2 was detected. The recorded time-of-flight spectra indicate that these internally excited radicals dissociated into Y+C2H4 in a concerted reaction with the first C-X bond rupture. Product anisotropy implies that the overall reaction time for three-body formation is in a fraction of rotational period. According to an asynchronous concerted reaction model, the measured spectra were simulated with product translational energy distributions coupled by asymmetric angular distributions. For the mixed halide, CH2BrCH2Cl, triple products Br+Cl+C2H4 can be originated from the cleavage of either the C-Br bond or the C-Cl bond. The results are discussed and where appropriate, comparisons with previous investigations of the related molecules are included. 相似文献
16.
17.
McCunn LR FitzPatrick BL Krisch MJ Butler LJ Liang CW Lin JJ 《The Journal of chemical physics》2006,125(13):133306
This paper examines the unimolecular dissociation of propargyl (HCCCH2) radicals over a range of internal energies to probe the CH+HCCH and C+C2H3 bimolecular reactions from the radical intermediate to products. The propargyl radical was produced by 157 nm photolysis of propargyl chloride in crossed laser-molecular beam scattering experiments. The H-loss and H2 elimination channels of the nascent propargyl radicals were observed. Detection of stable propargyl radicals gave an experimental determination of 71.5 (+5-10) kcal/mol as the lowest barrier to dissociation of the radical. This barrier is significantly lower than predictions for the lowest barrier to the radical's dissociation and also lower than calculated overall reaction enthalpies. Products from both H2+HCCC and H+C3H2 channels were detected at energies lower than what has been theoretically predicted. An HCl elimination channel and a minor C-H fission channel were also observed in the photolysis of propargyl chloride. 相似文献
18.
用光子计数技术系统地探测了F(^2P)原子与溴代甲烷等(CH~3Br、CH~2Br~2和CHBr~3)反应在各种压力下的可见区(300~900nm)化学发光,得到HF电子基态振动泛频跃迁及 Br~2(B)、BrF(B)、CHF(A)、CH(A) 等分子电子激发态跃迁的发射谱.求出HF(υ=3)转动温度为480K,计算机模拟光谱获得了Br~2(B)的振动布居.对比F与氯代甲烷反应的机理分析表明,初级反应主要是F提取形成HF,多级反应产生了电子激发态的产物分子. 相似文献
19.
Kurosaki Y 《The journal of physical chemistry. A》2006,110(39):11230-11236
Direct ab initio molecular dynamics calculations have been carried out for the molecular channel of the photodissociation of propanal, C2H5CHO --> C2H6 + CO, at the RMP2(full)/cc-pVDZ level of ab initio molecular orbital theory. The initial conditions were generated using the microcanonical sampling to put the excess energy randomly into all vibrational modes of the TS. Starting from the TS, a total of approximately 700 trajectories were numerically integrated for 100 fs. The obtained final energy distributions for the C2H6 and CO fragments and their relative translational motion were found to be quite similar to those obtained for the acetaldehyde reaction, CH3CHO --> CH4 + CO, in our previous study (Chem. Phys. Lett. 2006, 421, 549) despite the fact that the number of degree of freedom for C2H6 is larger than that for CH4. The coupling between the intrinsic reaction coordinate and one of the generalized normal modes orthogonal to it was predicted substantially strong around s = 1.4 amu(1/2) bohr, and it is expected that the energy flow out of C2H6 proceeds through this coupling. However, the obtained energy distributions strongly suggest that the coupling among the modes in C2H6 is quite small and the intramolecular energy redistribution does not occur efficiently in this molecule. 相似文献
20.
The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction. 相似文献