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1.
Quasiclassical trajectory calculations were performed to calculate rovibrational distributions of the nascent HF fragment in the photodissociation of vinyl fluoride at 193 nm. The trajectories were initiated at the transition states of the four-center (4C) and three-center (3C) HF elimination channels, using a microcanonical, quasiclassical normal-mode sampling. In general, the calculated distributions are in reasonably good agreement with experiment. In particular, the trajectory distributions show bimodal character, although not as pronounced as that observed experimentally. The calculations predict that the 3C and 4C distributions are rather similar to each other, which suggests that the low-J and high-J components of the rotational distributions cannot be specifically assigned to each of these channels. 相似文献
2.
《Chemical physics letters》1987,137(6):505-509
Product energy distributions are reported for 193 nm NH3 photodissociation. Velocity-aligned Doppler spectroscopy on the H-atom fragment reveals a “cold” kinetic energy distribution, indicating a high degree of NH2 internal excitation. Data are compared with the trajectory calculations of Rice, Raff and Thompson for NH3(X̃ 1A1) dissociation, and the reaction mechanism of Ashfold, Bennett and Dixon is discussed. 相似文献
3.
The CH fragment from the 193 nm photodissociation of CHCl is observed in a molecular beam experiment. This fragment is formed in the higher-energy dissociation pathway, the lower pathway involving formation of CCl. Both the CHCl parent molecule and the CH fragment were detected by laser-induced fluorescence. The 193 nm CHCl absorption cross section was estimated from the reduction of the CHCl signal as a function of the photolysis laser fluence. The CH internal state distribution was derived from the analysis of laser-induced fluorescence spectra of the A-X Deltav=0 sequence. A modest degree of rotational excitation was found in the CH fragment; the most probable rotational level is N=1, but the distribution has a tail extending to N>25. Also observed is a slight preference for formation of Lambda-doublets of A(") symmetry, which appears to increase with increasing rotational angular momentum N. Vibrationally excited CH was observed, and the degree of vibrational excitation was found to be low. The energy available to the photofragments is predominantly released as translational excitation. The preferential formation of A(") Lambda-doublets suggests that dissociation occurs through a nonlinear excited state. 相似文献
4.
Chang YP Brouard M Cireasa R Perkins T Seamons SA 《Physical chemistry chemical physics : PCCP》2011,13(18):8213-8229
Angular momentum orientation has been observed in the OH(X(2)Π, v = 0) fragments generated by circularly polarized photodissociation of H(2)O(2) at 193 nm and 248 nm. The magnitude and sign of the orientation are strongly dependent on the OH(X) photofragment rotational state. In addition to conventional laser induced fluorescence methods, Zeeman quantum beat spectroscopy has also been used as a complementary tool to probe the angular momentum orientation parameters. The measured orientation at 193 nm is attributed solely to photodissociation via the ?(1)A state, even though at this wavelength H(2)O(2) is excited near equally to both the ?(1)A and B(1)B electronic states. This observation is confirmed by measurements of the photofragment orientation at 248 nm, where access to the ?(1)A state dominates. Several possible mechanisms are discussed to explain the observed photofragment orientation, and a simple physical model is developed, which includes the effects of the polarization of the parent molecular rotation upon absorption of circularly polarized light. Good agreement between the experimental and simulation results is obtained, lending support to the validity of the model. It is proposed that photofragment orientation arises mainly from the coupling of the parent rotational angular momentum with that induced during photofragmentation. 相似文献
5.
Butadiene monoxide (BMO) undergoes the S(0)-->S(1) transition, involving the excitation of both pi and n electrons to pi(*) orbital, at 193 nm. After relaxing to the ground electronic state via internal conversion, BMO molecules undergo intramolecular rearrangement and subsequently dissociate to form unexpected OH radicals, which were detected state selectively by laser-induced fluorescence technique, and the energy state distribution was measured. OH is produced vibrationally cold, OH(nu(")=0,J(")), with the rotational population characterized by a rotational temperature of 456+/-70 K. The major portion (approximately 60%) of the available energy is partitioned into internal degrees of the photofragments, namely, vibration and rotation. A considerable portion (25%-35%) also goes to the relative translation of the products. The Lambda doublet and spin-orbit ratios of OH were measured to be nearly unity, implying statistical distribution of these states and, hence, no preference for any of the Lambda doublet (Lambda+ and Lambda-) and spin-orbit (Pi(3/2) and Pi(1/2)) states. Formation time of the nascent OH radical was measured to be <100 ns. Different products, such as crotonaldehyde and methyl vinyl ketone, were detected by gas chromatography as stable products of photodissociation. A reaction mechanism for the formation of all these photoproducts, transient and stable, is proposed. The multiple pathways by which these products can be formed have been theoretically optimized, and energies have been calculated. Absorption cross section of BMO at 193 nm was measured, and quantum yield of OH generation channel was also determined. 相似文献
6.
The dynamics of the 193 nm photodissociation of the CFCl and CFBr molecules have been investigated in a molecular beam experiment. The CFCl and CFBr parent molecules were generated by pyrolysis of CHFCl2 and CFBr3, respectively, and the CFCl and the CF photofragment were detected by laser fluorescence excitation. The 193 nm attenuation cross section of CFCl was determined from the reduction of the CF photofragment signal as a function of the photolysis laser fluence. The internal state distribution was derived from the analysis of laser fluorescence excitation spectra in the A 2Sigma+-X 2Pi band system. A very low degree of rotational excitation, with essentially equal A' and A" Lambda-doublet populations, and no vibrational excitation were found in the CF photofragment. The energy available to the photofragments is hence predominantly released as translational energy. The CF internal state distribution is consistent with the dissociation of a linear intermediate state. Considerations of CFCl electronic states suggest that a bent Rydberg state is initially excited. 相似文献
7.
We report a full-dimensional potential energy surface (PES) for the OH+NO(2) reaction based on fitting more than 55,000 energies obtained with density functional theory-B3LYP6-311G(d,p) calculations. The PES is invariant with respect to permutation of like nuclei and describes all isomers of HOONO, HONO(2), and the fragments OH+NO(2) and HO(2)+NO. Detailed comparison of the structures, energies, and harmonic frequencies of various stationary points on the PES are made with previous and present high-level ab initio calculations. Two hydrogen-bond complexes are found on the PES and confirmed by new ab initio CASPT2 calculations. Quasiclassical trajectory calculations of the cross sections for ground rovibrational OH+NO(2) association reactions to form HOONO and HONO(2) are done using this PES. The cross section to form HOONO is larger than the one to form HONO(2) at low collision energies but the reverse is found at higher energies. The enhancement of the HOONO complex at low collision energies is shown to be due, in large part, to the transient formation of a H-bond complex, which decays preferentially to HOONO. The association cross sections are used to obtain rate constants for formation of HOONO and HONO(2) for the ground rovibrational states in the high-pressure limit. 相似文献
8.
Yabushita A Hashikawa Y Ikeda A Kawasaki M Tachikawa H 《The Journal of chemical physics》2004,120(11):5463-5468
The TOF spectra of photofragment hydrogen atoms from the 193 nm photodissociation of amorphous ice at 90-140 K have been measured. The spectra consist of both a fast and a slow components that are characterized by average translational energies of 2k(B)T(trans)=0.39+/-0.04 eV (2300+/-200 K) and 0.02 eV (120+/-20 K), respectively. The incident laser power dependency of the hydrogen atom production suggests one-photon process. The electronic excitation energy of a branched cluster, (H(2)O)(6+1), has been theoretically calculated, where (H(2)O)(6+1) is a (H(2)O)(6) cyclic cluster attached by a water molecule with the hydrogen bond. The photoabsorption of this branched cluster is expected to appear at around 200 nm. The source of the hydrogen atoms is attributed to the photodissociation of the ice surface that is attached by water molecules with the hydrogen bond. Atmospheric implications are estimated for the photodissociation of the ice particles (Noctilucent clouds) at 190-230 nm in the region between 80 and 85 km altitude. 相似文献
9.
We observed fifteen photofragments upon photolysis of propenal (acrolein, CH(2)CHCHO) at 193 nm using photofragment translational spectroscopy and selective vacuum-ultraviolet (VUV) photoionization. All the photoproducts arise from nine primary and two secondary dissociation pathways. We measured distributions of kinetic energy of products and determined branching ratios of dissociation channels. Dissociation to CH(2)CHCO + H and CH(2)CH + HCO are two major primary channels with equivalent branching ratios of 33%. The CH(2)CHCO fragment spontaneously decomposes to CH(2)CH + CO. A proportion of primary products CH(2)CH from the fission of bond C-C of propenal further decompose to CHCH + H but secondary dissociation HCO → H + CO is negligibly small. Binary dissociation to CH(2)CH(2) (or CH(3)CH) + CO and concerted three-body dissociation to C(2)H(2) + CO + H(2) have equivalent branching ratios of 14%-15%. The other channels have individual branching ratios of ~1%. The production of HCCO + CH(3) indicates the formation of intermediate methyl ketene (CH(3)CHCO) and the production of CH(2)CCH + OH and CH(2)CC + H(2)O indicate the formation of intermediate hydroxyl propadiene (CH(2)CCHOH) from isomerization of propenal. Distributions of kinetic energy release and dissociation mechanisms are discussed. This work provides a complete look and profound insight into the multi-channel dissociation mechanisms of propenal. The combination of a molecular beam apparatus and synchrotron VUV ionization allowed us to untangle the complex mechanisms of nine primary and two secondary dissociation channels. 相似文献
10.
The photodissociation of allyl iodide (C3H5I) at 193 nm was investigated by using a combination of vacuum-ultraviolet photoionization of the allyl radical, resonant multiphoton ionization of the iodine atoms, and velocity map imaging. The data provide insight into the primary C-I bond fission process and into the dissociative ionization of the allyl radical to produce C3H3+. The experimental results are consistent with the earlier results of Szpunar et al. [J. Chem. Phys. 119, 5078 (2003)], in that some allyl radicals with internal energies higher than the secondary dissociation barrier are found to be stable. This stability results from the partitioning of available energy between the rotational and vibrational degrees of freedom of the radical, the effects of a centrifugal barrier along the reaction coordinate, and the effects of the kinetic shift in the secondary dissociation of the allyl radical. The present results suggest that the primary dissociation of allyl iodide to allyl radicals plus I*(2P(1/2)) is more important than previously suspected. 相似文献
11.
The photodissociation of isocyanic acid (HNCO) and ketene (CH2CO) at 193 nm was investigated using an ArF laser to dissociate the carbonyl compound and a CO laser to probe the resulting vibrationally excited CO. The dissociation of HNCO at 193 nm produces CO with an average vibrational energy of 4.6 ± 0.3 kcal/mol. The dissociation Gf CH2CO at 193 nm produces CO with an average vibrational energy of 6.4 ± 0.8 kcal/mol. The observed CO vibrational energy distributions were found to be in close agreement with those predicted statistically assuming NH(a 1Δ) + CO and CH2(1A1) + CO were the photodissociation products. 相似文献
12.
Brouard M Cireasa R Clark AP Quadrini F Vallance C 《Physical chemistry chemical physics : PCCP》2006,8(47):5549-5563
In the following paper we present translational anisotropy and angular momentum polarization data for O((3)P(1)) and O((3)P(2)) products of the photodissociation of molecular oxygen at 193 nm. The data were obtained using polarized laser photodissociation coupled with resonantly enhanced multiphoton ionization and velocity-map ion imaging. Under the jet-cooled conditions employed, absorption is believed to be dominated by excitation into the Herzberg continuum. The experimental data are compared with previous experiments and theoretical calculations at this and other wavelengths. Semi-classical calculations performed by Groenenboom and van Vroonhoven [J. Chem. Phys, 2002, 116, 1965] are used to estimate the alignment parameters arising from incoherent excitation and dissociation and these are shown to agree qualitatively well with the available experimental data. Following the work of Alexander et al. [J. Chem. Phys, 2003, 118, 10566], orientation and alignment parameters arising from coherent excitation and dissociation are modelled more approximately by estimating phase differences generated subsequent to dissociation via competing adiabatic pathways leading to the same asymptotic products. These calculations lend support to the view that large values of the coherent alignment moments, but small values of the corresponding orientation moments, could arise from coherent excitation of (and subsequent dissociation via) parallel and perpendicular components of the Herzberg I, II and III transitions. 相似文献
13.
Following photodissociation of fluorobenzene (C(6)H(5)F) at 193 nm, rotationally resolved emission spectra of HF(1相似文献
14.
Following photodissociation of formyl fluoride (HFCO) at 193 nm, we detected products with fragmentation translational spectroscopy utilizing a tunable vacuum ultraviolet beam from a synchrotron for ionization. Among three primary dissociation channels observed in this work, the F-elimination channel HFCO-->HCO+F dominates, with a branching ratio approximately 0.66 and an average release of kinetic energy approximately 55 kJ mol(-1); about 17% of HCO further decomposes to H+CO. The H-elimination channel HFCO-->FCO+H has a branching ratio approximately 0.28 and an average release of kinetic energy approximately 99 kJ mol(-1); about 21% of FCO further decomposes to F+CO. The F-elimination channel likely proceeds via the S1 surface whereas the H-elimination channel proceeds via the T1 surface; both channels exhibit moderate barriers for dissociation. The molecular HF-elimination channel HFCO-->HF+CO, correlating with the ground electronic surface, has a branching ratio of only approximately 0.06; the average translational release of 93 kJ mol(-1), approximately 15% of available energy, implies that the fragments are highly internally excited. Detailed mechanisms of photodissociation are discussed. 相似文献
15.
We compare the influence of the dilution of silane and disilane in nitrogen during laser photodissociation to produce silicon at 193 nm, at room temperature in a static reaction chamber. The experimental results show that the conversion of the reactant gas and its deposition yield can be controlled by varying adequately the extent of dilution. So, two total pressure regions have been observed, independent of the dilution: below 40–50 Torr, the variations of stable species concentration are very important but above these values the variation in the dilution rate has practically no effects on their concentrations. In the first region, during the silane photodissociation at the initial reactant pressure below 5 Torr, the conversion of silane increases with increasing dilution, and at higher initial reactant pressure the conversion of silane tends to rise only a little. In contrast, at any initial reactant pressure, the conversion of disilane during its photodecomposition decreases with increasing dilution. In the second region, the concentration of each stable gaseous species tends to reach a pressure stationary-state. For both the silane and disilane photodissociation, the deposition yield of silicon increases with decreasing the initial reactant gas pressure and it reaches a pressure stationary-state above 50% dilution; but in all the cases, it is greater in disilane photolysis than that of silane. A simple kinetic model is proposed for which the computed results predict the time-evolution of gas composition and amount of silicon deposited. 相似文献
16.
Infrared emission following the photolysis of SO(2) by a 193 nm laser pulse (20 ns duration) was recorded with 500 ns time and 10 cm(-1) spectral resolution. Spectral analyses of the time-resolved spectra revealed the vibrationally excited nascent SO population distribution as (v = 1)/(v = 2)/(v = 3)/(v = 4)/(v = 5) = 0.54 ± 0.04, 1.00 ± 0.03, 0.00 ± 0.03, 0.01 ± 0.03, and 0.10 ± 0.03. The nascent SO was found to be rotationally excited with an average rotational temperature around 1000 K for v = 1 and v = 2 levels and 300 K for the v = 5 level. The vibrationally excited SO likely originates from two distinct dissociation mechanisms; the v = 1 and 2 populations are generated through intersystem crossing between the C state and a repulsive state (2(3)A'), and the v = 5 population is generated through internal conversion from the C to the X state. Efficient V-V energy transfer from nascent vibrationally excited SO to SO(2)(ν(1)) is also observed. The appearance of the SO(2)(ν(1)) ν(1) = 2 emission, before that from the ν(1) = 1 population is consistent with the previous report that the Δν = -2 channel is more efficient than the Δν = -1 channel. 相似文献
17.
A recent experimental study [Houston, P. L.; Kable, S. H. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 16079] of the photodissociation of acetaldehyde (CH(3)CHO) has suggested two distinct mechanisms for the production of the molecular products CH(4) + CO. One corresponds to the traditional transition state mechanism and the other to a transition state-skirting path similar to the roaming channel previously reported in formaldehyde. To investigate this theoretically, a full-dimensional potential energy surface (PES) has been constructed. The PES was fit with permutationally invariant polynomials to 135,000 points calculated using coupled cluster theory with single and double excitations and a perturbative treatment of triple excitations [CCSD(T)] and correlation consistent basis sets of double- and triple-zeta quality. To test the accuracy of the PES additional CCSD(T) and multireference configuration interaction calculations were carried out. Quasiclassical trajectory calculations were run on the PES starting at the acetaldehyde equilibrium geometry and also at the conventional transition state (TS) for the molecular products CH(4) + CO. The former calculations agree well with the experimental results of Houston and Kable; however, those from the TS do not. The implications for a non-transition state, roaming mechanism in this molecule are discussed. 相似文献
18.
Unimolecular Rate Constants for the HF and HCl Elimination Reactions from Chemically Activated CF2ClSH
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Chemically activated CF3SH, CFCl2SH, and CF2ClSH were formed through combination of SH and CF3, CFCl2, and CF2Cl radicals, respectively. The SH radical was prepared by abstraction of an H‐atom from H2S by the halocarbon radical produced during photolysis of (CF3)2C=O, (CFCl2)2C=O, or (CF2Cl)2C=O. 1,2‐HX (X = F, Cl) elimination reactions were observed from CF3SH, CFCl2SH, and CF2ClSH with products detected by GC‐MS. The combination reaction of CF2Cl radicals with SH radicals prepared CF2ClSH molecules with approximately 318 kJ/mol of internal energy. The experimental rate constants for elimination of HCl and HF from CF2ClSH were 3 ± 3 × 1010 and 2 ± 1 × 109 s?1, respectively. Comparison to Rice–Ramsperger–Kassel–Marcus (RRKM) calculated rate constants assigned the threshold energies as 171 ± 12 and 205 ± 12 kJ/mol for the unimolecular elimination of HCl and HF, respectively. Theoretical calculations using the B3PW91, MP2, and M062X methods with the 6311+G(2d,p) and 6‐31G(d',p') basis sets established that for a specific method the threshold energies differ by only 4 kJ/mol between the two different basis sets. There was wide variation among the three methods, but the M062X approach appeared to give threshold energies closest to the experimental values. Chemically activated CF3SH and CFCl2SH were also prepared with about 318 kcal mol?1 of internal energy, and the HX (X = F, Cl) elimination reactions were observed. Only HCl loss was detected from CFCl2SH, but the rate was too fast to measure with our kinetic method; however, based on our detection limit the HF elimination channel is at least 50 times slower. 相似文献
19.
We performed a quasiclassical trajectory dynamics study on a model analytical 21-dimensional (7 active atoms) potential energy surface (PES) to examine in detail the mechanism of the hydrogen absorption in a simple (NaAlH(4))(2)Ti model system. The reaction involves a capture of H(2) by the Ti centre and formation of the (η(2)-H(2))Ti(NaAlH(3))(2) coordination complex containing the side-on bonded dihydrogen ligand. The calculated rate constant corresponds to a very fast capture of H(2) by the Ti coordination sphere without a demonstrable barrier. This implies that this step is not the rate-determining step in the complex multi-step process of the NaAlH(4) recovery. The model analytical PES captures the essence of this reaction well and the corresponding energy contours compare favourably to those based on the all-atom hybrid density functional theory calculations. 相似文献
20.
Following the photodissociation of o-fluorotoluene [o-C(6)H(4)(CH(3))F] at 193 nm, rotationally resolved emission spectra of HF(1< or =v< or =4) in the spectral region of 2800-4000 cm(-1) are detected with a step-scan Fourier transform spectrometer. HF(v< or =4) shows nearly Boltzmann-type rotational distributions corresponding to a temperature approximately 1080 K; a short extrapolation from data in the period of 0.5-4.5 mus leads to a nascent rotational temperature of 1130+/-100 K with an average rotational energy of 9+/-2 kJ mol(-1). The observed vibrational distribution of (v=1):(v=2):(v=3)=67.6: 23.2: 9.2 corresponds to a vibrational temperature of 5330+/-270 K. An average vibrational energy of 25+/-(3) (12) kJ mol(-1) is derived based on the observed population of HF(1< or =v< or =3) and estimates of the population of HF (v=0 and 4) by extrapolation. Experiments performed on p-fluorotoluene [p-C(6)H(4)(CH(3))F] yielded similar results with an average rotational energy of 9+/-2 kJ mol(-1) and vibrational energy of 26+/-(3) (12) kJ mol(-1) for HF. The observed distributions of internal energy of HF in both cases are consistent with that expected for four-center elimination. A modified impulse model taking into account geometries and displacement vectors of transition states during bond breaking predicts satisfactorily the rotational excitation of HF. An observed vibrational energy of HF produced from fluorotoluene slightly smaller than that from fluorobenzene might indicate the involvement of seven-membered-ring isomers upon photolysis. 相似文献