Overtone dissociation of peroxynitric acid (HO2NO2): absorption cross sections and photolysis products

Band strengths for the second (3nuOH) and third (4nuOH) overtones of the OH stretch vibration of peroxynitric acid, HO2NO2 (PNA) in the gas-phase were measured using Cavity Ring-Down Spectroscopy (CRDS). Both OH overtone transitions show diffuse smoothly varying symmetrical absorption profiles without observable rotational structure. Integrated band strengths (base e) at 296 K were determined to be S(3nuOH) = (5.7 +/- 1.1) x 10(-20) and S(4nuOH) = (4.9 +/- 0.9) x 10(-21) cm(2) molecule(-1) cm(-1) with peak cross sections of (8.8 +/- 1.7) x 10(-22) and (7.0 +/- 1.3) x 10(-23) cm(2) molecule(-1) at 10086.0 +/- 0.2 cm(-1) and 13095.8 +/- 0.4 cm(-1), respectively, using PNA concentrations measured on line by Fourier-transform infrared and ultraviolet absorption spectroscopy. The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors in the measurements. OH overtone spectra measured at lower temperature, 231 K, showed a narrowing of the 3nuOH band along with an increase in its peak absorption cross section, but no change in S(3nuOH) to within the precision of the measurement (+/-9%). Measurement of a PNA action spectrum showed that HO2 is produced from second overtone photodissociation. The action spectrum agreed with the CRDS absorption spectra. The PNA cross sections determined in this work for 3nuOH and 4nuOH will increase calculated atmospheric photolysis rates of PNA slightly.     

Effects of torsion on O-H stretch overtone spectra and direct overtone photolysis of methyl hydroperoxide

We use laser photoacoustic spectroscopy to obtain overtone spectra at three through six quanta of O-H stretch excitation (3nu(OH)-6nu(OH)) for methyl hydroperoxide (MeOOH). Extending the spectral regions beyond our previous work reveals new features that can be attributed to transitions involving torsion about the O-O bond. Experimental spectral profiles (3nu(OH)-6nu(OH)) and cross sections (3nu(OH)-5nu(OH)) at room temperature show a good agreement with the simulated spectra that we obtain from ab initio calculations employing a vibration-torsion model at 298 K. A Birge-Sponer analysis yields experimental values for the O-H stretch frequency (omega=3773+/-15 cm(-1)) and anharmonicity (omegax=94+/-3 cm(-1)). We also detect OH radicals by laser-induced fluorescence and present photodissociation action spectra of MeOOH in the regions of 4nu(OH) and 5nu(OH). While the spectral profile at 5nu(OH) mimics the photoacoustic spectrum, the peak intensity for transitions to torsionally excited states is relatively more intense in the action spectrum at 4nu(OH), reflecting the fact that the 4nu(OH) excitation energy is below the literature dissociation energy (D0=42.6+/-1 kcal mol(-1)) so that features in the action spectrum come from thermally populated excited states. Finally, we use our calculations to assign contributions to individual peaks in the room-temperature spectra and relate our findings to a recent dynamics study in the literature.     

IR signature of the photoionization-induced hydrophobic-->hydrophilic site switching in phenol-Arn clusters

IR spectra of phenol-Arn (PhOH-Arn) clusters with n=1 and 2 were measured in the neutral and cationic electronic ground states in order to determine the preferential intermolecular ligand binding motifs, hydrogen bonding (hydrophilic interaction) versus pi bonding (hydrophobic interaction). Analysis of the vibrational frequencies of the OH stretching motion, nuOH, observed in nanosecond IR spectra demonstrates that neutral PhOH-Ar and PhOH-Ar2 as well as cationic PhOH+-Ar have a pi-bound structure, in which the Ar atoms bind to the aromatic ring. In contrast, the PhOH+-Ar2 cluster cation is concluded to have a H-bound structure, in which one Ar atom is hydrogen-bonded to the OH group. This pi-->H binding site switching induced by ionization was directly monitored in real time by picosecond time-resolved IR spectroscopy. The pi-bound nuOH band is observed just after the ionization and disappears simultaneously with the appearance of the H-bound nuOH band. The analysis of the picosecond IR spectra demonstrates that (i) the pi-->H site switching is an elementary reaction with a time constant of approximately 7 ps, which is roughly independent of the available internal vibrational energy, (ii) the barrier for the isomerization reaction is rather low(<100 cm(-1)), (iii) both the position and the width of the H-bound nuOH band change with the delay time, and the time evolution of these spectral changes can be rationalized by intracluster vibrational energy redistribution occurring after the site switching. The observation of the ionization-induced switch from pi bonding to H bonding in the PhOH+-Ar2 cation corresponds to the first manifestation of an intermolecular isomerization reaction in a charged aggregate.     

Comparative study of the hydrogen-bonded complexes of phenol and o-cyanophenol with CO Ab initio and DFT approachs

The structures, stability and vibrational spectra of the hydrogen-bonded complexes of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) have been studied using ab initio and DFT calculations. Full geometry optimization has been performed for the studied complexes by DFT (BLYP/6-311++G(d,p)) calculations. The calculations show that the hydrogen-bond formation of carbon monoxide (CO) with phenol and o-cyanophenol (syn and anti) leads to the following stable structures: C6H5OH...CO (1A); C6H5OH...OC (1B); (syn) o-CNC6H4OH...CO (2A-syn); (syn) o-CNC6H4OH...OC (2B-syn); (anti) o-CNC6H4 OH...CO (2A-anti) and (anti) o-CNC6H4OH...OC (2B-anti). Having in mind the corrected values of the dissociation energy, the studied hydrogen-bonded complexes can be ordered according their stability as follows: 2A-anti>2A-syn>1A>2B-anti>1B>2B-syn. The predicted red-shifts for the nuOH vibration with the B3LYP/6-311++G(d,p) calculations for the structures 1A (-46 cm-1), 2A-syn (-60 cm-1) and 2A-anti (-73 cm-1) are in very good agreement with the experimentally observed. The magnitudes of the wavenumber shifts are indicative of relatively weak OH...C hydrogen-bonded interactions. The calculations predict an increase of the IR intensity of the nuOH vibration in the complexes 1A, 2A-anti and 2A-syn up to five times.     

Unimolecular processes in CH2OH below the dissociation barrier: O-H stretch overtone excitation and dissociation

The OH-stretch overtone spectroscopy and dynamics of the hydroxymethyl radical, CH(2)OH, are reported in the region of the second and third overtones, which is above the thermochemical threshold to dissociation to H+CH(2)O (D(0)=9600 cm(-1)). The second overtone spectrum at 10 484 cm(-1) is obtained by double resonance IR-UV resonance enhanced multiphoton ionization (REMPI) spectroscopy via the 3p(z) electronic state. It is rotationally resolved with a linewidth of 0.4 cm(-1) and displays properties of local-mode vibration. No dissociation products are observed. The third overtone spectra of CH(2)OH and CD(2)OH are observed at approximately 13 600 cm(-1) by monitoring H-atom photofragments while scanning the excitation laser frequency. No double resonance REMPI spectrum is detected, and no D fragments are produced. The spectra of both isotope analogs can be simulated with a linewidth of 1.3 cm(-1), indicating dissociation via tunneling. By treating the tunneling as one dimensional and using the calculated imaginary frequency, the barrier to dissociation is estimated at about 15 200 cm(-1), in good agreement with theoretical estimations. The Birge-Sponer plot is linear for OH-stretch vibrations 1nu(1)-4nu(1), demonstrating behavior of a one-dimensional Morse oscillator. The anharmonicity parameter derived from the plot is similar to the values obtained for other small OH containing molecules. Isomerization to methoxy does not contribute to the predissociation signal and the mechanism appears to be direct O-H fission via tunneling. CH(2)OH presents a unique example in which the reaction coordinate is excited directly and leads to predissociation via tunneling while preserving the local-mode character of the stretch vibration.     

Experimental infrared spectra of Cl-(ROH) (R = H, CH3, CH3CH2) complexes in the gas-phase

Infrared multiple photon dissociation spectra for the chloride ion solvated by either water, methanol or ethanol have been recorded using an FTICR spectrometer coupled to a free-electron laser, and are presented here along with assignments to the observed bands. The assignments made to the Cl(-)/H(2)O, Cl(-)(CH(3)OH), and Cl(-)(CH(3)CH(2)OH) spectra are based on comparison with the neutral H(2)O, CH(3)OH, and CH(3)CH(2)OH spectra, respectively. This work confirms that a band observed around 1400 cm(-1) in the Cl(-)(H(2)O) spectrum is not due to the Ar tag in Ar predissociation spectra. The carrier of this band is, most likely, the first overtone of the OHCl bend. Based on the position of the overtone in the IRMPD spectrum, 1375 cm(-1), the fundamental must occur very close to 700 cm(-1) and observation of this band should aid theoretical treatments of the spectrum of this complex. B3LYP/6-311++G(2df,2pd) calculations are shown to reproduce the IRMPD spectra of all three solvated chloride species. They also predict that attaching one or two Ar atoms to the Cl(-)(H(2)O) complex results in a shift of no more than a few wavenumbers in the fundamental bands for the bare complex, in agreement with previous experiment. For both alcohol-Cl(-) complexes, the S(N)2 "backside attack" isomers are not observed and Cl(-) is predicted theoretically, and confirmed experimentally, to be bound to the hydroxyl hydrogen. For Cl(-)(CH(3)CH(2)OH), the trans and gauche conformers are similar in energy, with the gauche conformer predicted to be thermodynamically favoured. The experimental infrared spectrum agrees well with that predicted for the gauche conformer but a mixture of gauche and anti conformers cannot be ruled out based on the experimental spectra nor on the computed thermochemistry.     

Rotamers of m-cresol cation studied by mass-analyzed threshold ionization spectroscopy

We have applied two-color resonant two-photon mass-analyzed threshold ionization technique to record the vibrational spectra of the selected rotamers of m-cresol. The adiabatic ionization energies of cis and trans m-cresol are determined to be 66,933+/-5 and 67,084+/-5 cm(-1), respectively. Frequencies of the in-plane ring vibrations 6a, 1, and 9b are measured to be 528, 720, 1167 cm(-1) for the cis and 520, 698, and 1153 cm(-1) for the trans m-cresol cation. This indicates that different orientation of the OH group with respect to the CH(3) group slightly influences these ring vibrations.     

HOD分子在(~C)1B1态的光解动力学:产物OH/OD的分支比以及OD键解离能

Photodissociation of jet-cooled HOD via the ? state around 124 nm has been studied using the H(D)-atom Rydberg tagging time-of-flight technique. Rotational state resolved action spectrum and the product translational energy distribution spectra have been recorded for both D+OH and H+OD dissociation channels. Product channel OH/OD branching ratios for the individual ?- X rotational transition have been determined. A comparison is also given with the B- X and ?- X transitions. In addition, the dissociation energy of the OD bond in HOD has been determined accurately to be 41751.3±5 cm^-1.     

Role of OH-stretch/torsion coupling and quantum yield effects in the first OH overtone spectrum of cis-cis HOONO

A joint theoretical and experimental investigation is undertaken to study the effects of OH-stretch/HOON torsion coupling and of quantum yield on the previously reported first overtone action spectrum of cis-cis HOONO (peroxynitrous acid). The minimum energy path along the HOON dihedral angle is computed at the coupled cluster singles and doubles with perturbative triples level with correlation consistent polarized quadruple zeta basis set, at the structure optimized using the triple zeta basis set (CCSD(T)/cc-pVQZ//CCSD(T)/cc-pVTZ). The two-dimensional ab initio potential energy and dipole moment surfaces for cis-cis HOONO are calculated as functions of the HOON torsion and OH bond length about the minimum energy path at the CCSD(T)/cc-pVTZ and QCISD/AUG-cc-pVTZ (QCISD-quadratic configuration interaction with single and double excitation and AUG-augmented with diffuse functions) level of theory/basis, respectively. The OH-stretch vibration depends strongly on the torsional angle, and the torsional potential possesses a broad shelf at approximately 90 degrees , the cis-perp conformation. The calculated electronic energies and dipoles are fit to simple functional forms and absorption spectra in the region of the OH fundamental and first overtone are calculated from these surfaces. While the experimental and calculated spectra of the OH fundamental band are in good agreement, significant differences in the intensity patterns are observed between the calculated absorption spectrum and the measured action spectrum in the 2nu(OH) region. These differences are attributed to the fact that several of the experimentally accessible states do not have sufficient energy to dissociate to OH+NO(2) and therefore are not detectable in an action spectrum. Scaling of the intensities of transitions to these states, assuming D(0)=82.0 kJ/mol, is shown to produce a spectrum that is in good agreement with the measured action spectrum. Based on this agreement, we assign two of the features in the spectrum to Deltan=0 transitions (where n is the HOON torsion quantum number) that are blue shifted relative to the origin band, while the large peak near 7000 cm(-1) is assigned to a series of Deltan=+1 transitions, with predominant contributions from torsionally excited states with substantial cis-perp character. The direct absorption spectrum of cis-cis HOONO (6300-6850 cm(-1)) is recorded by cavity ringdown spectroscopy in a discharge flow cell. A single band of HOONO is observed at 6370 cm(-1) and is assigned as the origin of the first OH overtone of cis-cis HOONO. These results imply that the origin band is suppressed by over an order of magnitude in the action spectrum, due to a reduced quantum yield. The striking differences between absorption and action spectra are correctly predicted by the calculations.     

OH-stretch vibrational spectroscopy of hydroxymethyl hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH(2)OOH) and its partially deuterated analogue, HOCD(2)OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1nu(OH) and 2nu(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH(2)OOH initiated by excitation of the 4nu(OH) and 5nu(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4nu(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.     

Protonation Preferentially Stabilizes Minor Tautomers of the Halouracils: IRMPD Action Spectroscopy and Theoretical Studies

Tautomerization induced by protonation of halouracils may increase their efficacy as anti-cancer drugs by altering their reactivity and hydrogen bonding characteristics, potentially inducing errors during DNA and RNA replication. The gas-phase structures of protonated complexes of five halouracils, including 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, and 6-chlorouracil are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical electronic structure calculations. IRMPD action spectra were measured for each complex in the IR fingerprint region extending from ~1000 to 1900?cm(-1) using the free electron laser (FELIX). Correlations are made between the measured IRMPD action spectra and the linear IR spectra for the stable low-energy tautomeric conformations computed at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level of theory. Absence of an intense band(s) in the IRMPD spectrum arising from the carbonyl stretch(es) that are expected to appear near 1825?cm(-1) provides evidence that protonation induces tautomerization and preferentially stabilizes alternative, noncanonical tautomers of these halouracils where both keto functionalities are converted to hydroxyl groups upon binding of a proton. The weak, but measurable absorption, which does occur for these systems near 1835?cm(-1) suggests that in addition to the ground-state conformer, very minor populations of excited, low-energy conformers that contain keto functionalities are also present in these experiments.     

Infrared overtone spectroscopy and unimolecular decay dynamics of peroxynitrous acid

Peroxynitrous acid (HOONO) is generated in a pulsed supersonic expansion through recombination of photolytically generated OH and NO(2) radicals. A rotationally resolved infrared action spectrum of HOONO is obtained in the OH overtone region at 6971.351(4) cm(-1) (origin), providing definitive spectroscopic identification of the trans-perp (tp) conformer of HOONO. Analysis of the rotational band structure yields rotational constants for the near prolate asymmetric top, the ratio of the a-type to c-type components of the transition dipole moment for the hybrid band, and a homogeneous linewidth arising from intramolecular vibrational energy redistribution and/or dissociation. The quantum state distribution of the OH (nu=0,J(OH)) products from dissociation is well characterized by a microcanonical statistical distribution constrained only by the energy available to products, 1304+/-38 cm(-1). This yields a 5667+/-38 cm(-1) [16.2(1) kcal mol(-1)] binding energy for tp-HOONO. An equivalent available energy and corresponding binding energy are obtained from the highest observed OH product state. Complementary high level ab initio calculations are carried out in conjunction with second-order vibrational perturbation theory to predict the spectroscopic observables associated with the OH overtone transition of tp-HOONO including its vibrational frequency, rotational constants, and transition dipole moment. The same approach is used to compute frequencies and intensities of multiple quantum transitions that aid in the assignment of weaker features observed in the OH overtone region, in particular, a combination band of tp-HOONO involving the HOON torsional mode.     

State-resolved unimolecular dissociation of cis-cis HOONO: Product state distributions and action spectrum in the 2nuOH band region

Nascent OH fragment product state distributions arising from unimolecular dissociation of room temperature HOONO, initiated by excitation in the region of the 2nu(OH) band, are probed using laser-induced fluorescence at sub-Doppler resolution. Phase-space simulations of the measured OH rotational distributions are consistent with the dissociation dynamics being statistical and confirm that all major features in the room temperature action spectrum belong to the cis-cis conformer. The phase-space simulations also allow us to estimate the HO-ONO bond dissociation energy of cis-cis HOONO to be D(0)=19.9+/-0.5 kcal/mol, which when combined with the known heat-of-formation data for the OH and NO(2) fragments gives DeltaH(f) (0)(cis-cis HOONO)=-2.5 kcal/mol. In addition to fragment energy release, spectral features in the cis-cis HOONO action spectrum are examined with respect to their shifts upon (15)N isotope substitution and through ab initio spectral simulation using a two-dimensional dipole surface that takes into account the influence of HOON torsional motion on the OH stretching overtone. The two-dimensional spectral simulations, using CCSD(T)/cc-pVTZ dipole surface, qualitatively reproduces features appearing in the action spectrum and suggest that the strong broad feature occurring approximately 570 cm(-1) to the blue of the cis-cis HOONO 2nu(OH) peak, likely involve excitation of HOON-torsion/OH-stretch combination bands originating from thermally populated excited torsional states. A closer examination of the predictions of the two-dimensional model with experiments also reveals its limitations and suggests that a more elaborate treatment, one which includes several additional modes, will likely be required in order to fully explain the room temperature action spectrum. Ab initio calculations of the HOON torsional potential at the CCSD(T)/cc-pVTZ level of theory are also presented and confirm that cis-perp configuration does not correspond to a bound localized minimum on the HOONO potential energy surface.     

Conformational stability, vibrational assignmenents, barriers to internal rotations and ab initio calculations of 2-aminophenol (d 0 and d3)

The Raman (3700-100 cm(-1)) and infrared (4000-400 cm(-1)) spectra of solid 2-aminophenol (2AP) have been recorded. The internal rotation of both OH and NH2 moieties produce ten conformers with either Cs or C1 symmetry. However, the calculated energies as well as the imaginary vibrational frequencies reduce rotational isomerism to five isomers. The molecular geometry has been optimized without any constraints using RHF, MP2 and B3LYP levels of theory at 6-31G(d), 6-311+G(d) and 6-31++G(d,p) basis sets. All calculations predict 1 (cis; OH is directed towards NH2) to be the most stable conformation except RHF/6-31++G(d,p) basis set. The 1 (cis) isomer is found to be more stable than 8 (trans; OH is away from the NH2 moiety and the NH bonds are out-of-plane) by 1.7 kcal/mol (598 cm(-1)) as obtained from MP2/6-31G(d) calculations. Aided by experimental and theoretical vibrational spectra, cis and trans 2AP are coexist in solution but cis isomer is more likely present in the crystalline state. Aided by MP2 and B3LYP frequency calculations, molecular force fields, simulated vibrational spectra utilizing 6-31G(d) basis set as well as normal coordinate analysis, complete vibrational assignments for HOC6H4NH2 and DOC6H4ND2 have been proposed. Furthermore, we carried out potential surface scan, to determine the barriers to internal rotations of NH2 and OH groups. All results are reported herein and compared with similar molecules when appropriate.     

Infrared action spectroscopy and dissociation dynamics of the HOOO radical

The HOOO radical has long been postulated to be an important intermediate in atmospherically relevant reactions and was recently deemed a significant sink for OH radicals in the tropopause region. In the present experiments, HOOO radicals are generated in a pulsed supersonic expansion by the association of O(2) and photolytically generated OH radicals, and the spectral signature and vibrational predissociation dynamics are investigated via IR action spectroscopy, an IR-UV double resonance technique. Rotationally resolved IR action spectra are obtained for trans-HOOO in the fundamental (nu(OH)) and overtone (2nu(OH)) OH stretching regions at 3569.30 and 6974.18 cm(-1), respectively. The IR spectra exhibit homogeneous line broadening, characteristic of a approximately 26-ps lifetime, which is attributed to intramolecular vibrational redistribution and/or predissociation to OH and O2 products. In addition, an unstructured feature is observed in both the OH fundamental and overtone regions of HOOO, which is likely due to cis-HOOO. The nascent OH X(2)Pi, v = 0 or v = 1, products following vibrational predissociation of HOOO, nu(OH) or 2nu(OH), respectively, have been investigated using saturated laser-induced fluorescence measurements. A distinct preference for population of Pi(A') Lambda-doublets in OH was observed and is indicative of a planar dissociation of trans-HOOO in which the symmetry of the bonding orbital is maintained.     

Conformation of L-tyrosine studied by fluorescence-detected UV-UV and IR-UV double-resonance spectroscopy

The laser-induced fluorescence spectrum of jet-cooled L-tyrosine exhibits more than 20 vibronic bands in the 35450-35750 cm(-1) region. We attribute these bands to eight conformers by using results of UV-UV hole-burning spectroscopy. These isomers are classified into four groups; each group consists of two rotational isomers that have a similar side-chain conformation but different orientations of the phenolic OH. The splitting of band origins of rotational isomers is 31, 21, 5, and 0 cm(-1) for these groups. IR-UV spectra suggest that conformers belonging to two of the four groups have an intramolecular OH...N hydrogen bond between the COOH and NH2 groups. By comparing experimental and theoretical results of L-tyrosine with those of L-phenylalanine, we propose probable conformers of L-tyrosine.     

Infrared plus vacuum ultraviolet spectroscopy of neutral and ionic methanol monomers and clusters: new experimental results

We present new observations of the infrared (IR) spectrum of neutral methanol and neutral and protonated methanol clusters employing IR plus vacuum ultraviolet (vuv) spectroscopic techniques. The tunable IR light covers the energy ranges of 2500-4500 cm(-1) and 5000-7500 cm(-1). The CH and OH fundamental stretch modes, the OH overtone mode, and combination bands are identified in the vibrational spectrum of supersonic expansion cooled methanol (2500-7500 cm(-1)). Cluster size selected IR plus vuv nonresonant infrared ion-dip infrared spectra of neutral methanol clusters, (CH(3)OH)(n) (n=2,[ellipsis (horizontal)],8), demonstrate that the methanol dimer has free and bonded OH stretch features, while clusters larger than the dimer display only hydrogen bonded OH stretch features. CH stretch mode spectra do not change with cluster size. These results suggest that all clusters larger than the dimer have a cyclic structure with OH groups involved in hydrogen bonding. CH groups are apparently not part of this cyclic binding network. Studies of protonated methanol cluster ions (CH(3)OH)(n)H(+) n=1,[ellipsis (horizontal)],7 are performed by size selected vuv plus IR photodissociation spectroscopy in the OH and CH stretch regions. Energies of the free and hydrogen bonded OH stretches exhibit blueshifts with increasing n, and these two modes converge to approximately 3670 and 3400 cm(-1) at cluster size n=7, respectively.     

Intermolecular vibrational mode of the benzoic acid dimer in solution observed by terahertz time-domain spectroscopy

The low-frequency modes of the benzoic acid (BA) dimer and its analogues in carbon tetrachloride (CCl(4)) have been investigated by terahertz time-domain spectroscopy. The solute spectrum is obtained by subtracting the solvent contribution from that of the solution. The difference spectrum of BA in CCl(4) has a broad band with a peak at 68 cm(-1). To assign the observed band, the spectrum is compared with spectra of other aromatic molecules, such as benzene and phenol in addition to p-methyl BA and deuterated BA species (BA-d(OH) and BA-d(5)) in CCl(4). The band at 68 cm(-1) is assigned to the cogwheel mode of the BA dimer. Density functional theory calculations also support this assignment. Finally, spectral lineshape analysis based on the multimode Brownian oscillator model is applied to the THz spectra for all the samples.     

Electronic and vibrational spectroscopy of intermediates in methane-to-methanol conversion by CoO+

At room temperature, cobalt oxide cations directly convert methane to methanol with high selectivity but very low efficiency. Two potential intermediates of this reaction, the [HO-Co-CH(3)](+) insertion intermediate and [H(2)O-Co=CH(2)](+) aquo-carbene complex are produced in a laser ablation source and characterized by electronic and vibrational spectroscopy. Reaction of laser-ablated cobalt cations with different organic precursors seeded in a carrier gas produces the intermediates, which subsequently expand into vacuum and cool. Ions are extracted into a time-of-flight mass spectrometer and spectra are measured via photofragment spectroscopy. Photodissociation of [HO-Co-CH(3)](+) in the visible and via infrared multiple photon dissociation (IRMPD) makes only Co(+) + CH(3)OH, while photodissociation of [H(2)O-Co=CH(2)](+) produces CoCH(2)(+) + H(2)O. The electronic spectrum of [HO-Co-CH(3)](+) shows progressions in the excited state Co-C stretch (335 cm(-1)) and O-Co-C bend (90 cm(-1)); the IRMPD spectrum gives ν(OH) = 3630 cm(-1). The [HO-Co-CH(3)](+)(Ar) complex has been synthesized and its vibrational spectrum measured in the O-H stretching region. The resulting spectrum is sharper than that obtained via IRMPD and gives ν(OH) = 3642 cm(-1). Also, an improved potential energy surface for the reaction of CoO(+) with methane has been developed using single point energies calculated by the CBS-QB3 method for reactants, intermediates, transition states and products.     

Predissociation spectroscopy of the argon-solvated H5O2+ "zundel" cation in the 1000-1900 cm(-1) region

Predissociation spectra of the H5O2+.Ar(1,2) cluster ions are reported in the 1000-1900 cm(-1) region. The weakly bound argon atoms enable investigation of the complex in a linear action mode, and the resulting spectra are much simpler than those reported previously in this region [Asmis et al., Science 299, 1375 (2003) and Fridgen et al., J. Phys. Chem. A 108, 9008 (2004)], which were obtained using infrared multiphoton dissociation of the bare complex. The observed spectrum consists of two relatively narrow bands at 1080 and 1770 cm(-1) that are likely due to excitation of the shared proton and intramolecular bending vibrations of the two water molecules, respectively. The narrow linewidths and relatively small (60 cm(-1)) perturbation introduced by the addition of a second argon atom indicate that the basic "zundel" character of the H5O2+ ion survives upon complexation.