Infrared photodissociation spectroscopy of vanadium oxide-carbonyl cations.

Mass selected vanadium oxide-carbonyl cations of the form VO(m)(CO)(n)(+) (m = 0-3 and n = 3-6) are studied via infrared laser photodissociation spectroscopy in the 600-2300 cm(-1) region. Insight into the structure and bonding of these complexes is obtained from the number of infrared active bands, their relative intensities and their frequency positions. Density functional theory calculations are carried out in support of the experimental data. The effect of oxidation on the carbonyl stretching frequencies of VO(CO)(n)(+), VO2(CO)(n)(+), and VO3(CO)(n)(+) complexes is investigated. All of these oxide-carbonyl species have C-O stretch vibrations blue-shifted from those of the pure vanadium ion carbonyls. The V-O stretches of these complexes are also investigated, revealing the effects of CO coordination on these vibrations. The oxide-carbonyls all have a hexacoordinate core analogous to that of V(CO)6(+). The fully coordinated vanadium monoxide-carbonyl species is VO(CO)5(+), and those of the dioxide and trioxide are VO2(CO)4(+) and VO3(CO)3(+), respectively.

IR spectroscopy of α- and ß-protonated pyrrole via argon complex photodissociation.

Protonated pyrrole cations are produced in a pulsed discharge/supersonic expansion source, mass-selected in a time-of-flight spectrometer, and studied with infrared photodissociation spectroscopy. Vibrational spectra in both the fingerprint and C-H/N-H stretching regions are obtained using the method of tagging with argon. Sharp vibrational structure is compared to IR spectra predicted by theory for the possible α-, ß-, and N-protonated structures. The spectral differences among these isomers are much larger than the frequency shifts due to argon attachment at alternative sites. Though α-protonation predominates thermodynamically, the kinetically favored ß-protonated species is also observed for the first time (in 3-4 times lower abundance under the conditions employed here). Theoretical investigations attribute the greater stability of α-protonated pyrrole to topological charge stabilization, rather than merely to the greater number of resonance contributors. The far-IR pattern of protonated pyrrole does not match the interstellar UIR bands.

Electronic spectroscopy of CoNe+ via mass-selected photodissociation.

The CoNe(+) diatomic cation is produced by laser vaporization in a pulsed-nozzle source and studied with photodissociation spectroscopy at visible wavelengths. Vibronic structure is assigned to the (3)Π(2) ← (3)Δ(3) band system correlating to the Co(+)((3)P(2) ← (3)F(4)) + Ne asymptote. The origin band (13,529 cm(-1)) and a progression of 14 other vibrational bands are detected ending in the dissociation limit at 14,191 cm(-1). The excited state dissociation energy is therefore D(0)(') = 662 cm(-1), and an energetic cycle using this, the origin band energy, and the atomic transition produces a ground state dissociation energy of D(0)(") = 930 cm(-1). The excited state vibrational frequency is 116.1 cm(-1). A rotationally resolved study of the origin band confirms the electronic transition assignment and provides the bond distance of r(0)(") = 2.36 Å. The properties of CoNe(+) are compared to those of other CoRG(+) and MNe(+) complexes studied previously.

Infrared spectroscopy and structures of cobalt carbonyl cations, Co(CO)n+ (n = 1-9).

Cobalt carbonyl cations of the form Co(CO)(n)(+) (n = 1-9) are produced in a molecular beam by laser vaporization in a pulsed nozzle source. These ions, and their corresponding "argon-tagged" analogues, Co(CO)(n)(Ar)(m)(+), are studied with mass-selected infrared photodissociation spectroscopy in the carbonyl stretching region. The number of infrared-active bands, their frequency positions, and their relative intensities provide distinctive patterns allowing determination of the geometries and electronic structures of these complexes. Co(CO)(5)(+) has a completed coordination sphere, consistent with its expected 18-electron stability, and it has the same structure (D(3h) trigonal bipyramid) as its neutral isoelectronic analog Fe(CO)(5). The carbonyl stretches in Co(CO)(5)(+) are less red-shifted than those in Fe(CO)(5) because of charge-induced reduction in the pi back-bonding. Co(CO)(1-4)(+) complexes have triplet ground states, but the spin changes to a singlet for the Co(CO)(5)(+) complex.

Infrared spectroscopy of gas phase benzenium ions: protonated benzene and protonated toluene, from 750 to 3400 cm-1.

Gas phase C 6H 7 (+) and C 7H 9 (+) ions are studied with infrared photodissociation spectroscopy (IRPD) and the method of rare gas tagging. The ions are produced in a pulsed electric discharge supersonic expansion source from benzene or toluene precursors. We observe exclusively the formation of either the C 2 v benzenium ion (protonated benzene) or the para isomer of the toluenium ion (protonated toluene). The infrared spectral signatures associated with each ion are established between 750 and 3400 cm (-1). Comparing the gas phase spectrum of the benzenium ion to the spectrum obtained in a superacid matrix [ Perkampus, H. H.; Baumgarten, E. Angew. Chem. Int. Ed. 1964, 3, 776 ], we find that the C 2 v structure of the gas phase species is minimally affected by the matrix environment. An intense band near 1610 cm (-1) is observed for both ions and is indicative of the allylic pi-electron density associated with the six membered ring in these systems. This spectral signature, also observed for alkyl substituted benzenium ions and protonated naphthalene, compares favorably with the interstellar, unidentified infrared emission band near 6.2 microm (1613 cm (-1)).

Structure of protonated carbon dioxide clusters: infrared photodissociation spectroscopy and ab initio calculations.

The infrared photodissociation spectra (IRPD) in the 700 to 4000 cm(-1) region are reported for H+ (CO2)n clusters (n = 1-4) and their complexes with argon. Weakly bound Ar atoms are attached to each complex upon cluster formation in a pulsed electric discharge/supersonic expansion cluster source. An expanded IRPD spectrum of the H+ (CO2)Ar complex, previously reported in the 2600-3000 cm(-1) range [Dopfer, O.; Olkhov, R.V.; Roth, D.; Maier, J.P. Chem. Phys. Lett. 1998, 296, 585-591] reveals new vibrational resonances. For n = 2 to 4, the vibrational resonances involving the motion of the proton are observed in the 750 to 1500 cm(-1) region of the spectrum, and by comparison to the predictions of theory, the structure of the small clusters are revealed. The monomer species has a nonlinear structure, with the proton binding to the lone pair of an oxygen. In the dimer, this nonlinear configuration is preserved, with the two CO2 units in a trans configuration about the central proton. Upon formation of the trimer, the core CO2 dimer ion undergoes a rearrangement, producing a structure with near C2v symmetry, which is preserved upon successive CO2 solvation. While the higher frequency asymmetric CO2 stretch vibrations are unaffected by the presence of the weakly attached Ar atom, the dynamics of the shared proton motions are substantially altered, largely due to the reduction in symmetry of each complex. For n = 2 to 4, the perturbation due to Ar leads to blue shifts of proton stretching vibrations that involve motion of the proton mostly parallel to the O-H+-O axis of the core ion. Moreover, proton stretching motions perpendicular to this axis exhibit smaller shifts, largely to the red. Ab initio (MP2) calculations of the structures, complexation energies, and harmonic vibrational frequencies are also presented, which support the assignments of the experimental spectra.

Infrared photodissociation spectroscopy of protonated acetylene and its clusters.

The protonated acetylene cation, C2H3+, (also known as the vinyl cation) and the proton-bound acetylene dimer cation (C4H5+) are produced by a pulsed supersonic nozzle/pulsed electrical discharge cluster source. The parent ions are also generated with weakly attached argon "tag" atoms, e.g., C2H3+Ar and C4H5+Ar. These ions are mass selected in a specially designed reflectron time-of-flight mass spectrometer and studied with infrared laser photodissociation spectroscopy in the 800-3600 cm-1 region. Vibrational resonances are detected for both ions in the C-H stretching region. C2H3+ has a strong vibrational resonance near 2200 cm-1 assigned to the bridged proton stretch of the nonclassical ion, while C4H5+ has no such free-proton vibration. Instead, C4H5+ has resonances near 1300 cm-1, consistent with a symmetrically shared proton in a di-bridged structure. Although the shared proton structure is not the lowest energy isomer of C4H5+, this species is apparently stabilized under the supersonic beam conditions. Larger clusters containing additional acetylene units are also investigated via the elimination of acetylene. These species have new IR bands indicating that rearrangement reactions have taken place to produce core C4H5+ ions with the methyl cyclopropane cation structure and/or the protonated cyclobutadiene isomer. Ab initio (MP2) calculations provide structures and predicted spectra consistent with all of these experiments.

Photodissociation of chromium oxide cluster cations.

Chromium oxide cluster cations, Cr(n)O(m)+, are produced by laser vaporization in a pulsed nozzle cluster source and detected with time-of-flight mass spectrometry. The mass spectrum exhibits a limited number of stoichiometries for each value of n, where m > n. The cluster cations are mass selected and photodissociated using the second (532 nm) or third (355 nm) harmonic output of a Nd:YAG laser. At either wavelength, multiphoton absorption is required to dissociate these clusters, which is consistent with their expected strong bonding. Cluster dissociation occurs via elimination of molecular oxygen, or by fission processes producing stable cation species and/or eliminating stable neutrals such as CrO3, Cr(2)O(5), or Cr(4)O(10). Specific cation clusters identified to be stable because they are produced repeatedly in the decomposition of larger clusters include Cr(2)O(4)+, Cr(3)O(6)+, Cr(3)O(7)+, Cr(4)O(9)+, and Cr(4)O(10)+.