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1.
2.
In this paper we present a theoretical study using time-dependent nonadiabatic reactant-product decoupling method for the state-to-state reactive scattering calculation of F((2)P(1/2))+H(2) (nu=j=0) reaction on the Alexander-Stark-Werner potential energy surface. In this nonadiabatic state-to-state calculation, the full wave function is partitioned into reactant component and a sum of all product components. The reactant and product components of the wave function are solved independently. For the excited state reaction, the state-to-state reaction probabilities for J=0.5 are calculated. Comparing the state-to-state reaction probabilities, it is found that the vibrational population of the HF product is dominated by vibrational levels nu=2 and 3. The rotation specific reaction probabilities of HF product in j=1 and 2 are larger than those in other rotational levels. As the rotation quantum number j increases, the positions of the peak in the rotational reaction probability of HF product in nu=3 shift to higher collision energy.  相似文献   

3.
The title reaction was investigated under crossed-beam conditions at three different collision energies, E(c) = 8.4, 2.76 and 1.46 kcal mol(-1). The combination of using a (2 + 1) resonance-enhanced multiphoton ionization for tagging state-specific CD(3) products and exploiting a time-sliced velocity imaging for ion detection allows us to reveal the coincident information of the two product pairs in a state-correlated manner. The pair-correlated results are reported for the two product vibrators -- (v(2) = 0, v'), (v(2) = 1, v'), (v(2) = 2, v') and (v(2) = 3, v')-and the dynamics attributes we examined include product state distributions, energy disposals and angular distributions. Together with our earlier communications, a rather complete picture of the correlated dynamics of the title reaction emerges. One of the major findings, the anti-correlated excitations of the two product vibrators at all four energies of this study, can qualitatively be understood by kinematics arguments.  相似文献   

4.
The state-to-state vibrational predissociation (VP) dynamics of the hydrogen-bonded ammonia-acetylene dimer were studied following excitation in the asymmetric CH stretch. Velocity map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated product energy distributions. Following vibrational excitation of the asymmetric CH stretch fundamental, ammonia fragments were detected by 2 + 1 REMPI via the B1E' <-- X1A1' and C'1A1' <-- X1A1' transitions. The fragments' center-of-mass (c.m.) translational energy distributions were determined from images of selected rotational levels of ammonia with one or two quanta in the symmetric bend (nu2 umbrella mode) and were converted to rotational-state distributions of the acetylene co-fragment. The latter is always generated with one or two quanta of bending excitation. All the distributions could be fit well when using a dimer dissociation energy of D0 = 900 +/- 10 cm(-1). Only channels with maximum translational energy <150 cm(-1) are observed. The rotational excitation in the ammonia fragments is modest and can be fit by temperatures of 150 +/- 50 and 50 +/- 20 K for 1nu2 and 2nu2, respectively. The rotational distributions in the acetylene co-fragment pair-correlated with specific rovibrational states of ammonia appear statistical as well. The vibrational-state distributions, however, show distinct state specificity among channels with low translational energy release. The predominant channel is NH3(1nu2) + C2H2(2nu4 or 1nu4 + 1nu5), where nu4 and nu5 are the trans- and cis-bend vibrations of acetylene, respectively. A second observed channel, with much lower population, is NH3(2nu2) + C2H2(1nu4). No products are generated in which the ammonia is in the vibrational ground state or the asymmetric bend (1nu4) state, nor is acetylene ever generated in the ground vibrational state or with CC stretch excitation. The angular momentum (AM) model of McCaffery and Marsh is used to estimate impact parameters in the internal collisions that give rise to the observed rotational distributions. These calculations show that dissociation takes place from bent geometries, which can also explain the propensity to excite fragment bending levels. The low recoil velocities associated with the observed channels facilitate energy exchange in the exit channel, which results in statistical-like fragment rotational distributions.  相似文献   

5.
Photofragment yield spectra and NO(X(2)Pi(1/2,3/2); v = 1, 2, 3) product vibrational, rotational, and spin-orbit state distributions were measured following NO dimer excitation in the 4000-7400 cm(-1) region in a molecular beam. Photofragment yield spectra were obtained by monitoring NO(X(2)Pi; v = 1, 2, 3) dissociation products via resonance-enhanced multiphoton ionization. New bands that include the symmetric nu(1) and asymmetric nu(5) NO stretch modes were observed and assigned as 3nu(5), 2nu(1) + nu(5), nu(1) + 3nu(5), and 3nu(1) + nu(5). Dissociation occurs primarily via Deltav = -1 processes with vibrational energy confined preferentially to one of the two NO fragments. The vibrationally excited fragments are born with less rotational energy than predicted statistically, and fragments formed via Deltav = -2 processes have a higher rotational temperature than those produced via Deltav = -1 processes. The rotational excitation likely derives from the transformation of low-lying bending and torsional vibrational levels in the dimer into product rotational states. The NO spin-orbit state distribution reveals a slight preference for the ground (2)Pi(1/2) state, and in analogy with previous results, it is suggested that the predominant channel is X(2)Pi(1/2) + X(2)Pi(3/2). It is suggested that the long-range potential in the N-N coordinate is the locus of nonadiabatic transitions to electronic states correlating with excited product spin-orbit states. No evidence of direct excitation to electronic states whose vertical energies lie in the investigated energy region is obtained.  相似文献   

6.
Using a Chebyshev wave packet method, total and state-resolved reaction probabilities (J=0) were calculated for the reactions of C(1D) with various hydrogen isotopomers (H2, D2, and HD, nu i=0, j i=0) on a recent ab initio potential energy surface. For all the isotopic variants, it was found that the initial state specified reaction probabilities have no energy threshold and are strongly oscillatory, indicative of the involvement of long-lived resonances in this barrierless reaction. The J=0 product vibrational and rotational distributions for all three isotopic reactions, and the CH/CD branching ratio for the C+HD reaction, show strong dependence on the collision energy, further underscoring the important role played by the resonances. The generally decaying vibrational distributions and highly excited rotational distributions, which corroborate an insertion mechanism, and the dominance of the CD+H channel in the C+HD reaction are consistent with existing experimental observations. Initial state specified integral cross sections and rate constants were estimated using a capture model. The estimated rate constants were found to be close and in the order kHD>kH2>kD2. Finally, a method to calculate branching ratio in the C+HD reaction is proposed.  相似文献   

7.
The probability per collision P(T) of near-resonant vibration-to-vibration energy transfer (ET) of one quantum of vibrational energy from vibrational levels nu=8 and nu=9 of OH to N(2)(nu=0), OH(nu)+N(2)(0)-->OH(nu-1)+N(2)(1), is calculated in the 100-350 K temperature range. These processes represent important steps in a model that explains the enhanced 4.3 microm emission from CO(2) in the nocturnal mesosphere. The calculated energy transfer is mediated by weak long-range dipole-quadrupole interaction. The results of this calculation are very sensitive to the strength of the two transition moments. Because of the long range of the intermolecular potential, the resonance function, a measure of energy that can be efficiently exchanged between translation and vibration-rotation degrees of freedom, is rather narrow. A narrow resonance function coupled with the large rotational constant of OH is shown to render the results of the calculation very sensitive to the rotational distribution, or the rotational temperature if one exists, of this molecule. The calculations are carried out in the first and second orders of perturbation theory with the latter shown to give ET probabilities that are an order of magnitude larger than the former. The reasons for the difference in magnitude and temperature dependence of the first- and second-order calculations are discussed. The results of the calculations are compared with room temperature measurements as well as with an earlier calculation. Our calculated results are in good agreement with the room temperature measurements for the transfer of vibrational energy for the exothermic OH(nu=9) ET process but are about an order lower than the room temperature measurements for the exothermic OH(nu=8) ET process. The cause of this discrepancy is explored. This calculation does not give the large values of the rate coefficients needed by the model that explains the enhanced 4.3 microm emission from CO(2) in the nocturnal mesosphere.  相似文献   

8.
We report the first rotationally resolved spectroscopic studies on PH3+(X2A2") using zero kinetic energy photoelectron spectroscopy and coherent VUV radiation. The spectra about 8000 cm(-1) above the ground vibrational state of PH3+(X2A2") have been recorded. We observed the vibrational energy level splittings of PH3+(X2A2") due to the tunneling effect in the inversion (symmetric bending) vibration (nu2+). The energy splitting for the first inversion vibrational state (0+/0-) is 5.8 cm(-1). The inversion vibrational energy levels, rotational constants, and adiabatic ionization energies (IEs) for nu2+ = 0-16 have been determined. The bond angles between the neighboring P-H bonds and the P-H bond lengths are also obtained using the experimentally determined rotational constants. With the increasing of the inversion vibrational excitations (nu2+), the bond lengths (P-H) increase a little and the bond angles (H-P-H) decrease a lot. The inversion vibrational energy levels have also been calculated by using one dimensional potential model and the results are in good agreement with the experimental data for the first several vibrational levels. In addition to inversion vibration, we also observed firstly the other two vibrational modes: the symmetric P-H stretching vibration (nu1+) and the degenerate bending vibration (nu4+). The fundamental frequencies for nu1+ and nu4+ are 2461.6 (+/-2) and 1043.9 (+/-2) cm(-1), respectively. The first IE for PH3 was determined as 79670.9 (+/-1) cm(-1).  相似文献   

9.
A beam containing CH(4), Cl(2), and He is expanded into a vacuum chamber where CH(4) is prepared via infrared excitation in a combination band consisting of one quantum of excitation each in the bending and torsional modes (nu(2)+nu(4)). The reaction is initiated by fast Cl atoms generated by photolysis of Cl(2) at 355 nm, and the resulting CH(3) and HCl products are detected in a state-specific manner using resonance-enhanced multiphoton ionization (REMPI). By comparing the relative amplitudes of the action spectra of Cl+CH(4)(nu(2)+nu(4)) and Cl+CH(4)(nu(3)) reactions, we determine that the nu(2)+nu(4) mode-driven reaction is at least 15% as reactive as the nu(3) (antisymmetric stretch) mode-driven reaction. The REMPI spectrum of the CH(3) products shows no propensity toward the formation of umbrella bend mode excited methyl radical, CH(3)(nu(2)=1), which is in sharp distinction to the theoretical expectation based on adiabatic correlations between CH(4) and CH(3). The rotational distribution of HCl(v=1) products from the Cl+CH(4)(nu(2)+nu(4)) reaction is hotter than the corresponding distribution from the Cl+CH(4)(nu(3)) reaction, even though the total energies of the two reactions are the same within 4%. An explanation for this enhanced rotational excitation of the HCl product from the Cl+CH(4)(nu(2)+nu(4)) reaction is offered in terms of the projection of the bending motion of the CH(4) reagent onto the rotational motion of the HCl product. The angular distributions of the HCl(nu=0) products from the Cl+CH(4)(nu(2)+nu(4)) reaction are backward scattered, which is in qualitative agreement with theoretical calculation. Overall, nonadiabatic product vibrational correlation and mode specificity of the reaction indicate that either the bending mode or the torsional mode or both modes are strongly coupled to the reaction coordinate.  相似文献   

10.
采用准经典轨线方法研究了在不同碰撞能下,碰撞反应N(4S)+NO(X2Π)→ N2(X3Σg- )+O(3P)在两个最低势能面3A 和 3A'上产物与反应物之间的矢量相关. 结果表明,对于不同的碰撞能,在两个势能面上反应产物的转动取向展示了不同的特征和趋势. 随着碰撞能的增加,发生在3A 势能面上的反应主要受外平面机理支配,而发生在 3A' 势能面上的反应倾向于受内平面机理支配. 这些差异来自于两个势能面的不同构型.  相似文献   

11.
High-resolution photofragment translational spectroscopy is used in this work to measure the translational and internal energy distributions in the CD3 and iodine fragments produced from the photodissociation of CD3I at 266 and 304 nm. Channel selected detection, via resonantly enhanced multiphoton ionization, combined with one-dimensional core sampling provides detailed information about vibrational state distributions of the CD3 fragments. The vibrational state distributions of CD3 fragments in the I*(2P12) channel have a propensity of nu2 ' umbrella bending mode with a maximum at nu2 ' = 1 for 266 nm photodissociation. For I*(2P12) channel at 304 nm photodissociation, vibrational state distributions of CD3 fragment have a maximum in the vibrational ground state. For the I(2P32) channel (1Q1 <-- 3Q(0+)), nu2 ' umbrella bending vibrational distribution is measured as the predominant vibrational mode but has a much broader distribution when compared to that of the I* channel. The vibrational state distributions of the CD3 fragment produced from the perpendicular transition, i.e., 3Q1, which was determined at 304 nm photodissociation, has a maximum at nu2 ' = 1. The curve crossing possibility between the 1Q1 and 3Q(0+) adiabatic potentials is determined as 0.19 for 266 and 0.85 for 304 nm. The trend in reaction dynamics in 266 and 304 nm photodissociation of CD3I is compared with theoretical calculations. A bond dissociation energy D0(C-I) = 56.60+/-0.5 kcal/mol was derived by applying laws of energy conservation.  相似文献   

12.
High-resolution infrared spectra of the clusters N2O-(ortho-D2)N and N2O-(HD)N, N=1-4, isolated in bulk solid parahydrogen at liquid helium temperatures are studied in the 2225 cm-1 region of the nu3 antisymmetric stretch of N2O. The clusters form during vapor deposition of separate gas streams of a precooled hydrogen mixture (ortho-D2para-H2 or HDpara-H2) and N2O onto a BaF2 optical substrate held at approximately 2.5 K in a sample-in-vacuum liquid helium cryostat. The cluster spectra reveal the N2O nu3 vibrational frequency shifts to higher energy as a function of N, and the shifts are larger for ortho-D2 compared to HD. These vibrational shifts result from the reduced translational zero-point energy for N2O solvated by the heavier hydrogen isotopomers. These spectra allow the N=0 peak at 2221.634 cm-1, corresponding to the nu3 vibrational frequency of N2O isolated in pure solid parahydrogen, to be assigned. The intensity of the N=0 absorption feature displays a strong temperature dependence, suggesting that significant structural changes occur in the parahydrogen solvation environment of N2O in the 1.8-4.9 K temperature range studied.  相似文献   

13.
First principles model calculations of the vibration-to-vibration (VV) energy transfer (ET) processes NO(+)(nu=1)+N(2)(nu=n-1)-->NO(+)(nu=0)+N(2)(nu=n)+(28.64n-14.67) cm(-1) and NO(+)(nu=n)+N(2)(nu=0)-->NO(+)(nu=n-1)+N(2)(nu=1)+(32.52(n-1)+13.97) cm(-1) for n=1-3 in the 300-1000 K temperature range are performed. The VV ET probability is computed for three mechanisms: (1) The charge on NO(+) acting on the average polarizability of N(2) induces a dipole moment in N(2) which then interacts with the permanent dipole moment of NO(+) to mediate the energy transfer. (2) The charge on NO(+) acting on the anisotropic polarizability of N(2) induces a dipole moment in N(2) which then interacts with the permanent dipole moment of NO(+) to mediate the energy transfer. (3) The dipole moment of NO(+) interacts with the quadrupole moment of N(2) to mediate the energy transfer. Because the probability amplitudes of the second and third mechanisms add coherently the ET probability for these two mechanisms is given as a single number. The probability of energy transfer per collision is in the 5 x 10(-3) range. The results of this calculation are compared with the available experimental data. This calculation should help quantify the role of NO(+) in the energy budget of the upper atmosphere.  相似文献   

14.
Photodissociation studies using ion imaging are reported, measuring the coherence of the polarization of the S((1)D(2)) fragment from the photolysis of single-quantum state-selected carbonyl sulfide (OCS) at 223 and 230 nm. A hexapole state-selector focuses a molecular beam of OCS parent molecules in the ground state (nu2=0mid R:JM=10) or in the first excited bending state (nu2=1mid R:JlM=111). At 230 nm photolysis the Im[a1 (1)(parallel, perpendicular)] moment for the fast S(1D2) channel increases by about 50% when the initial OCS parent state changes from the vibrationless ground state to the first excited bending state. No dependence on the initial bending state is found for photolysis at 223 nm. We observe separate rings in the slow channel of the velocity distribution of S(1D2) correlating to single CO(J) rotational states. The additional available energy for photolysis at 223 nm is found to be channeled mostly into the CO(J) rotational motion. An improved value for the OC-S bond energy D0=4.292 eV is reported.  相似文献   

15.
The ionization of a beam of H2 Rydberg molecules in collision with a metal surface (evaporated Au or Al) is studied. The Rydberg states are excited in an ultraviolet-vacuum ultraviolet double-resonant process and are state selected with a core rotational quantum number N+=0 or 2 and principal quantum numbers n=17-22 (N+=2) or n=41-45 (N+=0). It is found that the N+=0 states behave in a very similar manner to previous studies with atomic xenon Rydberg states, the distance of ionization from the surface scaling with n2. The N+=2 states, however, undergo a process of surface-induced rotational autoionization in which the core rotational energy transfers to the Rydberg electron. In this case the ionization distance scales approximately with nu0(2), the effective principal quantum number with respect to the adiabatic threshold. This process illustrates the close similarity between field ionization in the gas phase and the surface ionization process which is induced by the field due to image charges in the metal surface. The surface ionization rate is enhanced at certain specific values of the field, which is applied in the time interval between excitation and surface interaction. It is proposed here that these fields correspond to level crossings between the N+=0 and N+=2 Stark manifolds. The population of individual states of the N+=2, n=18 Stark manifold in the presence of a field shows that the surface-induced rotational autoionization is more facile for the blueshifted states, whose wave function is oriented away from the surface, than for the redshifted states. The observed processes appear to show little dependence on the chemical nature of the metallic surface, but a significant change occurs when the surface roughness becomes comparable to the Rydberg orbit dimensions.  相似文献   

16.
The dissociation of the hydroxymethyl radical, CH(2)OH, and its isotopolog, CD(2)OH, following excitation in the 4ν(1) region (OH stretch overtone, near 13,600 cm(-1)) was studied using sliced velocity map imaging. A new vibrational band near 13,660 cm(-1) arising from interaction with the antisymmetric CH stretch was discovered for CH(2)OH. In CD(2)OH dissociation, D atom products (correlated with CHDO) were detected, providing the first experimental evidence of isomerization in the CH(2)OH ? CH(3)O (CD(2)OH ? CHD(2)O) system. Analysis of the H (D) fragment kinetic energy distributions shows that the rovibrational state distributions in the formaldehyde cofragments are different for the OH bond fission and isomerization pathways. Isomerization is responsible for 10%-30% of dissociation events in all studied cases, and its contribution depends on the excited vibrational level of the radical. Accurate dissociation energies were determined: D(0)(CH(2)OH → CH(2)O + H) = 10,160 ± 70 cm(-1), D(0)(CD(2)OH → CD(2)O + H) = 10,135 ± 70 cm(-1), D(0)(CD(2)OH → CHDO + D) = 10,760 ± 60 cm(-1).  相似文献   

17.
We present the results of our product branching studies of the OH + C(2)D(4) reaction, beginning at the CD(2)CD(2)OH radical intermediate of the reaction, which is generated by the photodissociation of the precursor molecule BrCD(2)CD(2)OH at 193 nm. Using a crossed laser-molecular beam scattering apparatus with tunable photoionization detection, and a velocity map imaging apparatus with VUV photoionization, we detect the products of the major primary photodissociation channel (Br and CD(2)CD(2)OH), and of the secondary dissociation of vibrationally excited CD(2)CD(2)OH radicals (OH, C(2)D(4)/CD(2)O, C(2)D(3), CD(2)H, and CD(2)CDOH). We also characterize two additional photodissociation channels, which generate HBr + CD(2)CD(2)O and DBr + CD(2)CDOH, and measure the branching ratio between the C-Br bond fission, HBr elimination, and DBr elimination primary photodissociation channels as 0.99:0.0064:0.0046. The velocity distribution of the signal at m/e = 30 upon 10.5 eV photoionization allows us to identify the signal from the vinyl (C(2)D(3)) product, assigned to a frustrated dissociation toward OH + ethene followed by D-atom abstraction. The relative amount of vinyl and Br atom signal shows the quantum yield of this HDO + C(2)D(3) product channel is reduced by a factor of 0.77 ± 0.33 from that measured for the undeuterated system. However, because the vibrational energy distribution of the deuterated radicals is lower than that of the undeuterated radicals, the observed reduction in the water + vinyl product quantum yield likely reflects the smaller fraction of radicals that dissociate in the deuterated system, not the effect of quantum tunneling. We compare these results to predictions from statistical transition state theory and prior classical trajectory calculations on the OH + ethene potential energy surface that evidenced a roaming channel to produce water + vinyl products and consider how the branching to the water + vinyl channel might be sensitive to the angular momentum of the β-hydroxyethyl radicals.  相似文献   

18.
The title reaction was studied in a crossed-beam experiment by imaging of state-selected products. The rotational state selection of the CD(3) products was achieved using (2+1) resonance-enhanced multiphoton ionization. The coincident information on the DF coproducts was revealed in a state-resolved manner from time-sliced velocity map images. Significant dependences of both the correlated differential cross sections and the DF vibrational branching ratios on the "tagged" CD(3) rotation states were found. The dynamical implications of one of the major findings are discussed.  相似文献   

19.
Mass-resolved two-photon (1+1) resonance-enhanced multiphoton ionization spectra of the ~A-X transitions of various methylamine isotopomers (CH(3)NHD, CD(3)NH(2), CD(3)NHD, and CD(3)ND(2)) cooled in the supersonic jet expansion have been measured and analyzed. The band analysis using the Hamiltonian for the internal and overall rotational motions provides the accurate vibrational band positions, allowing for unambiguous assignments for all observed vibrational bands of methylamine isotopomers in the ~A states. Amino wagging (nu(9)) and methyl rocking (nu(7)) modes are found to be Franck-Condon active, and associated anharmonicity constants are precisely determined to give the detailed shape of the potential energy surface in the vicinity of the minimum electronic molecular structure. The barrier height for the nearly free internal rotation about the C-N bond in the ~A state is calculated to be strongly dependent on the excitation of the other higher-frequency vibrational modes, and it is found that the trend is consistent with the experiment. Experimentally measured spectroscopic constants are compared with ab initio calculations, confirming all vibronic assignments. Experimental and theoretical results on all possible HD isotopomers of methylamine in this work, with the earlier report on CH(3)NH(2) and CH(3)ND(2) Baek et al., [J. Chem. Phys. 118, 11026 (2003)], provide the complete spectroscopic characterization of the A state of methylamine.  相似文献   

20.
Parity resolved state-to-state cross sections for inelastic scattering of OH (X2Pi) by HCl were measured in a crossed molecular beam experiment at the collision energy of 920 cm(-1). The OH (X2Pi) radicals were prepared in a single quantum state, Omega=3/2, J=3/2, MJ=3/2, f, by means of electrostatic state selection in a hexapole field. The rotational distribution of the scattered OH radicals by HCl was probed by saturated LIF spectroscopy of the 0-0 band of the A 2Sigma+ - X 2Pi transition. Relative state-to-state cross sections were measured for rotational excitations up to J=9/2 within the Omega=3/2 spin-orbit manifold and up to J=7/2 within the Omega=1/2 spin-orbit manifold. A propensity for spin-orbit conserving transitions was found, but no propensity for excitation into a particular Lambda-doublet component of the same rotational state was evident. The data are presented and discussed in comparison with results previously obtained for collisions of OH with CO (Ecoll=450 cm(-1)) and N2 (Ecoll=410 cm(-1)) and with new data we have measured for the OH+CO system at a comparable collision energy (Ecoll=985 cm(-1)). This comparison suggests that the potential energy surface (PES) governing the interaction between OH and HCl is more anisotropic than the PES's governing the intermolecular interaction of OH with CO and N2.  相似文献   

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