Vibrational relaxation of methane by oxygen collisions: measurements of the near-resonant energy transfer between CH4 and O2 at low temperature

Vibrational relaxation in methane-oxygen mixtures has been investigated by means of a time-resolved pump-probe technique. Methane molecules are excited into selected rotational levels by tuning the pump laser to 2nu3 lines. The time evolution in population of various vibrational levels after the pumping pulse is monitored by probing, near 3000 cm-1, stretching transitions between various polyads like 2nu3(F2) - nu3, (nu3+2nu4) - 2nu4, and (nu3+nu4) - nu4 transitions. Measurements were performed from room temperature down to 190 K. A numerical kinetic model, taking into account the main collisional processes connecting energy levels up to 6000 cm(-1), has been developed to describe the vibrational relaxation. The model allows us to reproduce the observed signals and to determine rate coefficients of relaxation processes occurring upon CH4-O2 collisions. For the vibrational energy exchange, the rate coefficient of transfer from O2 (v = 1) to CH4 is found equal to (1.32 +/- 0.09) x 10(-12) cm3 molecule-1 s(-1) at 296 K and to (1.50 +/- 0.08) x 10(-12) cm3 molecule(-1) s(-1) at 193 K.     

Combined vacuum ultraviolet laser and synchrotron pulsed field ionization study of CH2BrCl

The pulsed field ionization-photoelectron (PFI-PE) spectrum of bromochloromethane (CH2BrCl) in the region of 85,320-88,200 cm-1 has been measured using vacuum ultraviolet laser. The vibrational structure resolved in the PFI-PE spectrum was assigned based on ab initio quantum chemical calculations and Franck-Condon factor predictions. At energies 0-1400 cm-1 above the adiabatic ionization energy (IE) of CH2BrCl, the Br-C-Cl bending vibration progression (nu1+=0-8) of CH2BrCl+ is well resolved and constitutes the major structure in the PFI-PE spectrum, whereas the spectrum at energies 1400-2600 cm-1 above the IE(CH2BrCl) is found to exhibit complex vibrational features, suggesting perturbation by the low lying excited CH2BrCl+(A 2A") state. The assignment of the PFI-PE vibrational bands gives the IE(CH2BrCl)=85,612.4+/-2.0 cm-1 (10.6146+/-0.0003 eV) and the bending frequencies nu1+(a1')=209.7+/-2.0 cm-1 for CH2BrCl+(X2A'). We have also examined the dissociative photoionization process, CH2BrCl+hnu-->CH2Cl++Br+e-, in the energy range of 11.36-11.57 eV using the synchrotron based PFI-PE-photoion coincidence method, yielding the 0 K threshold or appearance energy AE(CH2Cl+)=11.509+/-0.002 eV. Combining the 0 K AE(CH2Cl+) and IE(CH2BrCl) values obtained in this study, together with the known IE(CH2Cl), we have determined the 0 K bond dissociation energies (D0) for CH2Cl+-Br (0.894+/-0.002 eV) and CH2Cl-Br (2.76+/-0.01 eV). We have also performed CCSD(T, full)/complete basis set (CBS) calculations with high-level corrections for the predictions of the IE(CH2BrCl), AE(CH2Cl+), IE(CH2Cl), D0(CH2Cl+-Br), and D0(CH2Cl-Br). The comparison between the theoretical predictions and experimental determinations indicates that the CCSD(T, full)/CBS calculations with high-level corrections are highly reliable with estimated error limits of <17 meV.     

Vacuum ultraviolet laser pulsed field ionization-photoelectron study of allyl radical CH2CHCH2

The pulsed field ionization-photoelectron (PFI-PE) spectrum of allyl radical CH2CHCH2 (C3H5) in the energy range of 65 200-66 600 cm-1 has been measured using vacuum ultraviolet laser. Based on the simulation of the rotational structures resolved in the vibrational PFI-PE bands of C3H5+(X 1A1;0(0+) and nu7+=1), the ionization energies (IEs) of C3H5(X 2A2;0(0)) to form C3H5+(X 1A1;0(0+) and nu7+=1) are determined to be 65 584.6+/-2.0 cm-1 (8.131 46+/-0.000 25 eV) and 66 020.9+/-2.0 cm-1 (8.185 56+/-0.000 25 eV), respectively, where nu7+(a1) is the symmetric C-C-C bending mode of C3H5+(X 1A1). These values are compared to IE(C3H5) values obtained in previous experimental and high-level ab initio quantum theoretical studies.     

Infrared spectra and ab initio calculations for the F- -(CH4)n (n = 1-8) anion clusters

Infrared spectra of mass-selected F- -(CH4)n (n = 1-8) clusters are recorded in the CH stretching region (2500-3100 cm-1). Spectra for the n = 1-3 clusters are interpreted with the aid of ab initio calculations at the MP2/6-311++G(2df 2p) level, which suggest that the CH4 ligands bind to F- by equivalent, linear hydrogen bonds. Anharmonic frequencies for CH4 and F--CH4 are determined using the vibrational self-consistent field method with second-order perturbation theory correction. The n = 1 complex is predicted to have a C3v structure with a single CH group hydrogen bonded to F-. Its spectrum exhibits a parallel band associated with a stretching vibration of the hydrogen-bonded CH group that is red-shifted by 380 cm-1 from the nu1 band of free CH4 and a perpendicular band associated with the asymmetric stretching motion of the nonbonded CH groups, slightly red-shifted from the nu3 band of free CH4. As n increases, additional vibrational bands appear as a result of Fermi resonances between the hydrogen-bonded CH stretching vibrational mode and the 2nu4 overtone and nu2+nu4 combination levels of the methane solvent molecules. For clusters with n < or = 8, it appears that the CH4 molecules are accommodated in the first solvation shell, each being attached to the F- anion by equivalent hydrogen bonds.     

Atmospheric chemistry of CF3CH=CH2 and C4F9CH=CH2: products of the gas-phase reactions with Cl atoms and OH radicals

FTIR-smog chamber techniques were used to study the products of the Cl atom and OH radical initiated oxidation of CF3CH=CH2 in 700 Torr of N2/O2, diluent at 296 K. The Cl atom initiated oxidation of CF3CH=CH2 in 700 Torr of air in the absence of NOx gives CF3C(O)CH2Cl and CF3CHO in yields of 70+/-5% and 6.2+/-0.5%, respectively. Reaction with Cl atoms proceeds via addition to the >C=C< double bond (74+/-4% to the terminal and 26+/-4% to the central carbon atom) and leads to the formation of CF3CH(O)CH2Cl and CF3CHClCH2O radicals. Reaction with O2 and decomposition via C-C bond scission are competing loss mechanisms for CF3CH(O)CH2Cl radicals, kO2/kdiss=(3.8+/-1.8)x10(-18) cm3 molecule-1. The atmospheric fate of CF3CHClCH2O radicals is reaction with O2 to give CF3CHClCHO. The OH radical initiated oxidation of CxF2x+1CH=CH2 (x=1 and 4) in 700 Torr of air in the presence of NOx gives CxF2x+1CHO in a yield of 88+/-9%. Reaction with OH radicals proceeds via addition to the >C=C< double bond leading to the formation of CxF2x+1C(O)HCH2OH and CxF2x+1CHOHCH2O radicals. Decomposition via C-C bond scission is the sole fate of CxF2x+1CH(O)CH2OH and CxF2x+1CH(OH)CH2O radicals. As part of this work a rate constant of k(Cl+CF3C(O)CH2Cl)=(5.63+/-0.66)x10(-14) cm3 molecule-1 s-1 was determined. The results are discussed with respect to previous literature data and the possibility that the atmospheric oxidation of CxF2x+1CH=CH2 contributes to the observed burden of perfluorocarboxylic acids, CxF2x+1COOH, in remote locations.     

Reaction dynamics of Ca(4s3d 1D2)+CH4-->CaH(X 2Sigma+)+CH3: reaction pathway and energy disposal for the CaH product

The reaction pathway for Ca(4s3d 1D2)+CH4-->CaH(X 2Sigma+)+CH3 has been investigated by using a pump-probe technique in combination with potential-energy surface (PES) calculations. The nascent product distributions of CaH have been characterized with Boltzmann rotational temperatures of 1013+/-102 and 834+/-70 K for the v=0 and 1 levels, respectively, and a Boltzmann vibrational temperature of 1313+/-173 K. The rotational and vibrational energy partitions in CaH have been estimated to be 461+/-45 and 252+/-15 cm(-1), respectively. According to the PES calculations, the pathway favors an insertion mechanism. Ca(3 1D2) approaches CH4 along an attractive potential surface in a C2v (or Cs) symmetry and then the collision complex undergoes nonadiabatic transition to the reactive ground-state surface. An Arrhenius plot shows a potential-energy requirement of 2695+/-149 cm(-1), which accounts for the endothermicity of 2930 cm(-1) for the reaction scheme. The Ca-C bond distance in the transition state structure is short enough to allow for tight orbital overlap between CaH and CH3. The strong coupling between the moieties renders the energy transfer sufficient from CaH into the CH3 radical. As compared to the Ca(4 1P1) reaction, the dissociation lifetime of the intermediate complex with less excess energy is prolonged so as to cause much less vibrational energy disposal into CaH.     

Comparing the dynamical effects of symmetric and antisymmetric stretch excitation of methane in the Cl+CH4 reaction

The effects of two nearly isoenergetic C-H stretching motions on the gas-phase reaction of atomic chlorine with methane are examined. First, a 1:4:9 mixture of Cl(2), CH(4), and He is coexpanded into a vacuum chamber. Then, either the antisymmetric stretch (nu(3)=3019 cm(-1)) of CH(4) is prepared by direct infrared absorption or the infrared-inactive symmetric stretch (nu(1)=2917 cm(-1)) of CH(4) is prepared by stimulated Raman pumping. Photolysis of Cl(2) at 355 nm generates fast Cl atoms that initiate the reaction with a collision energy of 1290+/-175 cm(-1) (0.16+/-0.02 eV). Finally, the nascent HCl or CH(3) products are detected state-specifically via resonance enhanced multiphoton ionization and separated by mass in a time-of-flight spectrometer. We find that the rovibrational distributions and state-selected differential cross sections of the HCl and CH(3) products from the two vibrationally excited reactions are nearly indistinguishable. Although Yoon et al. [J. Chem. Phys. 119, 9568 (2003)] report that the reactivities of these two different types of vibrational excitation are quite different, the present results indicate that the reactions of symmetric-stretch excited or antisymmetric-stretch excited methane with atomic chlorine follow closely related product pathways. Approximately 37% of the reaction products are formed in HCl(v=1,J) states with little rotational excitation. At low J states these products are sharply forward scattered, but become almost equally forward and backward scattered at higher J states. The remaining reaction products are formed in HCl(v=0,J) and have more rotational excitation. The HCl(v=0,J) products are predominantly back and side scattered. Measurements of the CH(3) products indicate production of a non-negligible amount of umbrella bend excited methyl radicals primarily in coincidence with the HCl(v=0,J) products. The data are consistent with a model in which the impact parameter governs the scattering dynamics.     

Imaging the state-specific vibrational predissociation of the C2H2-NH3 hydrogen-bonded dimer

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.     

Jet-cooled infrared spectroscopy in slit supersonic discharges: symmetric and antisymmetric CH2 stretching modes of fluoromethyl (CH2F) radical

The combination of shot noise-limited direct absorption spectroscopy with long-path-length slit supersonic discharges has been used to obtain first high-resolution infrared spectra for jet-cooled CH2F radicals in the symmetric (nu1) and antisymmetric (nu5) CH2 stretching modes. Spectral assignment has yielded refined lower- and upper-state rotational constants and fine-structure parameters from least-squares fits to the sub-Doppler line shapes for individual transitions. The rotational constants provide indications of large amplitude vibrational averaging over a low-barrier double minimum inversion-bending potential. This behavior is confirmed by high-level coupled cluster singles/doubles/triples calculations extrapolated to the complete basis set limit and adiabatically corrected for zero point energy. The calculations predict a nonplanar equilibrium structure (theta approximately 29 degrees, where theta is defined to be 180 degrees minus the angle between the C-F bond and the CH2 plane) with a 132 cm(-1) barrier to planarity and a vibrational bend frequency (nu(bend) approximately 276 cm(-1)), in good agreement with previous microwave estimates (nu(bend) = 300 (30) cm(-1)) by Hirota and co-workers [Y. Endo et al., J. Chem. Phys. 79, 1605 (1983)]. The nearly 2:1 ratio of absorption intensities for the symmetric versus antisymmetric bands is in good agreement with density functional theory calculations, but in sixfold contrast with simple local mode CH2 bond dipole predictions of 1:3. This discrepancy arises from a surprisingly strong dependence of the symmetric stretch intensity on the inversion bend angle and provides further experimental support for a nonplanar equilibrium structure.     

Reaction dynamics and vibrational spectroscopy of CH3D molecules with both C-H and C-D stretches excited

State-resolved reactions of CH3D molecules containing both C-H and C-D stretching excitation with Cl atoms provide new vibrational spectroscopy and probe the consumption and disposal of vibrational energy in the reactions. The vibrational action spectra have three different components, the combination of the C-H symmetric stretch and the C-D stretch (nu1 + nu2), the combination of the C-D stretch and the C-H antisymmetric stretch (nu2 + nu4), and the combination of the C-D stretch and the first overtone of the CH3 bend (nu2 + 2nu5). The simulation for the previously unanalyzed (nu2 + nu4) state yields a band center of nu0 = 5215.3 cm(-1), rotational constants of A = 5.223 cm(-1) and B = 3.803 cm(-1), and a Coriolis coupling constant of zeta = 0.084. The reaction dynamics largely follow a spectator picture in which the surviving bond retains its initial vibrational excitation. In at least 80% of the reactive encounters of vibrationally excited CH3D with Cl, cleavage of the C-H bond produces CH2D radicals with an excited C-D stretch, and cleavage of the C-D bond produces CH3 radicals with an excited C-H stretch. Deviations from the spectator picture seem to reflect mixing in the initially prepared eigenstates and, possibly, collisional coupling during the reaction.     

Kinetic study of vibrational energy transfer from a wide range of vibrational levels of O2(X(3)Sigma(g)-, v = 6-12) to CF4

A wide range of vibrational levels of O2(X(3)Sigma(g)(-), v = 6-13) generated in the ultraviolet photolysis of O3 was selectively detected by the laser-induced fluorescence (LIF) technique. The time-resolved LIF-excited B(3)Sigma(u)(-)-X(3)Sigma(g)(-) system in the presence of CF4 has been recorded and analyzed by the integrated profiles method (IPM). The IPM permitted us to determine the rate coefficients k(v)(CF4) for vibrational relaxation of O2(X(3)Sigma(g)(-), v = 6-12) by collisions with CF4. Energy transfer from O2 (v = 6-12) to CF4 is surprisingly efficient compared to that of other polyatomic relaxation partners studied so far. The k(v)(CF4) increases with vibrational quantum number v from [1.5 +/- 0.2(2sigma)] x 10(-12) for v = 6 to [7.3 +/- 1.5(2sigma)] x 10(-11) for v = 12, indicating that the infrared-active nu3 vibrational mode of CF4 mainly governs the energy transfer with O2(X(3)Sigma(g)(-), v = 6-12). The correlation between the rate coefficients and fundamental infrared intensities has been discussed based on a comparison of the efficiency of energy transfer by several collision partners.     

Jahn-Teller effect in tetrahedral symmetry: large-amplitude tunneling motion and rovibronic structure of CH4+ and CD4+

The energy level structures of the ground vibronic states of 12CH4+, 13CH4+, and 12CD4+ have been measured by pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopy. The nuclear spin symmetries of the tunneling-rotational levels have been determined in double-resonance experiments via selected rotational levels of the v3=1 and v3=2 vibrational levels of the X 1A1 ground state of CH4. The energy level structures of 12CH4+, 13CH4+, and 12CD4+ have been analyzed with an effective tunneling-rotational Hamiltonian. The analysis together with a group theoretical treatment of the Tx(e+t2) Jahn-Teller effect in the Td(M) group prove that the equilibrium geometry of 12CH4+, 13CH4+, and 12CD4+ has C2v symmetry and characterize the pseudorotational dynamics in these fluxional cations. The tunneling behavior is discussed in terms of the relevant properties of the potential energy surface, some of which have been recalculated at the CCSD(T)/cc-pVTZ level of ab initio theory.     

State-resolved reactivity of CH4(2nu3) on Pt(111) and Ni(111): effects of barrier height and transition state location

Quantum state-resolved sticking coefficients on Pt(111) and Ni(111) surfaces have been measured for CH4 excited to the first overtone of the antisymmetric C-H stretch (2nu3) at well-defined kinetic energies in the range of 10-90 kJ/mol. The ground-state reactivity of CH4 is approximately 3 orders of magnitude lower on Ni(111) than on Pt(111) for kinetic energies in the range of 10-64 kJ/mol, reflecting a difference in barrier height of 28+/-6 kJ/mol. 2nu3 excitation of CH4 increases its reactivity by more than 4 orders of magnitude on Ni(111), whereas on Pt(111) the reactivity increase is lower by 2 orders of magnitude. We discuss the observed differences in the state-resolved reactivity for the ground state and 2nu3 excited state of methane in terms of a difference in barrier height and transition state location for the dissociation reaction on the two metal surfaces.     

Distribution of internal states of CO from O (1D) + CO determined with time-resolved fourier transform spectroscopy

Following collisions of O (1D) with CO, rotationally resolved emission spectra of CO (1 < or = v < or = 6) in the spectral region 1800-2350 cm(-1) were detected with a step-scan Fourier transform spectrometer. O (1D) was produced by photolysis of O3 with light from a KrF excimer laser at 248 nm. Upon irradiation of a flowing mixture of O3 (0.016 Torr) and CO (0.058 Torr), emission of CO (v < or = 6) increases with time, reaches a maximum approximately 10 micros. At the earliest applicable period (2-3 micros), the rotational distribution of CO is not Boltzmann; it may be approximately described with a bimodal distribution corresponding to temperatures approximately 8000 and approximately 500 K, with the proportion of these two components varying with the vibrational level. A short extrapolation from data in the period 2-6 micros leads to a nascent rotational temperature of approximately 10170 +/- 600 K for v = 1 and approximately 1400 +/- 40 K for v = 6, with an average rotational energy of 33 +/- 6 kJ mol(-1). Absorption by CO (v = 0) in the system interfered with population of low J levels of CO (v = 1). The observed vibrational distribution of (v = 2):(v = 3):(v = 4):(v = 5):(v = 6) = 1.00:0.64:0.51:0.32:0.16 corresponds to a vibrational temperature of 6850 +/- 750 K. An average vibrational energy of 40 +/- 4 kJ mol(-1) is derived based on the observed population of CO (2 < or = v < or = 6) and estimates of the population of CO (v = 0, 1, and 7) by extrapolation. The observed rotational distributions of CO (1 < or = v < or = 3) are consistent with results of previous experiments and trajectory calculations; data for CO (4 < or = v < or = 6) are new.     

Rovibrational energy transfer in the 4nu(CH) manifold of acetylene, viewed by IR-UV double-resonance spectroscopy. 4. Collision-induced quasi-continuous background effects

The 4nu(CH) rovibrational manifold around 12 700 cm(-1) in the electronic ground state, X, of acetylene (C2H2) is monitored by time-resolved infrared-ultraviolet double-resonance (IR-UV DR) spectroscopy. An IR laser pulse initially prepares rotational J states, associated with the "IR-bright" (nu1 + 3nu3) or (1 0 3 0 0)0 vibrational combination level, and subsequent collision-induced state-to-state energy transfer is probed by UV laser-induced fluorescence. Anharmonic, l-resonance, and Coriolis couplings affect the J states of interest, resulting in a congested rovibrational manifold that exhibits complex intramolecular dynamics. In preceding papers in this series, we have described three complementary forms of the IR-UV DR experiment (IR-scanned, UV-scanned, and kinetic) on collision-induced rovibrational satellites, comprising both regular even-DeltaJ features and unexpected odd-DeltaJ features. This paper examines an unusual collision-induced quasi-continuous background (CIQCB) effect that is apparently ubiquitous, accompanying regular even-DeltaJ rovibrational energy transfer and accounting for much of the observed collision-induced odd-DeltaJ satellite structure; certain IR-bright (1 0 3 0 0)0 rovibrational states (e.g., J = 12) are particularly prominent in this regard. We examine the mechanism of this CIQCB phenomenon in terms of a congested IR-dark rovibrational manifold that is populated by collisional transfer from the nearly isoenergetic IR-bright (1 0 3 0 0)0 submanifold.     

Imaging the nonadiabatic dynamics of the CH3 + HCl reaction

LAB-frame velocity distributions of Cl-atoms produced in the photoinitiated reaction of CH(3) radicals with HCl have been measured for both the ground Cl ((2)P(3/2)) and excited Cl* ((2)P(1/2)) spin-orbit states using a DC slice velocity-map ion imaging technique. The similarity of these distributions, as well as the average internal excitation of methane co-products for both Cl and Cl* pathways, suggest that all the reactive flux proceeds through the same transition state on the ground potential energy surface (PES) and that the couplings which promote nonadiabatic transitions to the excited PES correlating to Cl* occur later in the exit channel, beyond the TS region. The nature of these couplings is discussed in light of initial vibrational excitation of CH(3) radicals as well as previously reported nonadiabatic reactivity in other polyatomic molecule reactions. Furthermore, the scattering of the reaction products, derived using the photoloc method, suggests that at the high collision energy of our experiment (E(coll) = 22.3 kcal mol(-1)), large impact parameter collisions are favoured with a reduced kinematic constraint on the internal excitation of the methane co-product.     

Quasiclassical trajectory study of energy transfer and collision-induced dissociation in hyperthermal Ar + CH4 and Ar + CF4 collisions

We present a study of energy transfer in collisions of Ar with methane and perfluoromethane at hyperthermal energies (E(coll) = 4-10 eV). Quasiclassical trajectory calculations of Ar + CX(4) (X = H, F) collisions indicate that energy transfer from reagents' translation to internal modes of the alkane molecule is greatly enhanced by fluorination. The reasons for the enhancement of energy transfer upon fluorination are shown to emerge from a decrease in the hydrocarbon vibrational frequencies of the CX(4) molecule with increasing the mass of the X atom, and to an increase of the steepness of the Ar-CX(4) intermolecular potential. At high collision energies, we find that the cross section of Ar + CF(4) collisions in which the amount of energy transfer is larger than needed to break a C-F bond is at least 1 order of magnitude larger than the cross sections of Ar + CH(4) collisions producing CH(4) with energy above the dissociation limit. In addition, collision-induced dissociation is detected in short time scales in the case of the fluorinated species at E(coll) = 10 eV. These results suggest that the cross section for degradation of fluorinated hydrocarbon polymers under the action of nonreactive hyperthermal gas-phase species might be significantly larger than that of hydrogenated hydrocarbon polymers. We also illustrate a practical way to derive intramolecular potential energy surfaces for bond-breaking collisions by improving semiempirical Hamiltonians based on grids of high-quality ab initio calculations.     

Study of the H-F stretching band in the absorption spectrum of (CH3)2O...HF in the gas phase

The absorption spectra of the (CH3)2O...HF complex in the range of 4200-2800 cm(-1) were recorded in the gas phase at a resolutions of 0.1 cm(-1) at T = 190-340 K. The spectra obtained were used to analyze their structure and to determine the temperature dependencies of the first and second spectral moments. The band shape of the (CH3)2O...HF complex in the region of the nu1(HF) stretching mode was reconstructed nonempirically. The nu1 and nu3 stretching vibrations and four bending vibrations responsible for the formation of the band shape were considered. The equilibrium geometry and the 1D-4D potential energy surfaces were calculated at the MP2 6-311++G(2d,2p) level with the basis set superposition error taken into account. On the basis of these surfaces, a number of one- and multidimensional anharmonic vibrational problems were solved by the variational method. Solutions of auxiliary 1D and 2D vibrational problems showed the strong coupling between the modes. The energy levels, transition frequencies and intensities, and the rotational constants for the combining vibrational states necessary to reconstruct the spectrum were obtained from solutions of the 4D problem (nu1, nu3, nu5(B2), nu6(B2)) and the 2D problem (nu5(B1), nu6(B1)). The theoretical spectra reconstructed for different temperatures as a superposition of rovibrational bands associated with the fundamental, hot, sum, and difference transitions reproduce the shape and separate spectral features of the experimental spectra. The calculated value of the nu1 frequency is 3424 cm(-1). Along with the frequencies and absolute intensities, the calculation yields the vibrationally averaged values of the separation between the centers of mass of the monomers Rc.-of-m., R(O...F), and r(HF) for different states. In particular, upon excitation of the nu1 mode, Rc.-of-m. becomes shorter by 0.0861 A, and r(HF) becomes longer by 0.0474 A.