Charge-Transfer Spectroscopy of Ag+(Benzene) and Ag+(Toluene).

Gas-phase ion-molecule complexes of silver cation with benzene or toluene are produced via laser vaporization in a pulsed supersonic expansion. These ions are mass-selected and photodissociated with tunable UV-visible lasers. In both cases, photodissociation produces the organic cation as the only fragment via a metal-to-ligand charge-transfer process. The wavelength dependence of the photodissociation produces electronic spectra of the charge-transfer process. Broad structureless spectra result from excitation to the repulsive wall of the charge-transfer excited states. Additional transitions are detected correlating to the forbidden 1S → 1D silver cation-based atomic resonance and to the HOMO-LUMO excitation on the benzene or toluene ligand. Transitions to these states produce the same molecular cation photofragments produced in the charge-transfer transitions, indicating an unanticipated excited-state curve-crossing mechanism. Spectra measured for these ions are compared to those for ions tagged with argon atoms. The presence of argon causes a significant shift on the energetic positions of these electronic transitions for both Ag+(benzene) and Ag+(toluene).

Photodissociation Spectroscopy and Photofragment Imaging to Probe Fe+(Benzene)1,2 Dissociation Energies.

Tunable laser photodissociation spectroscopy measurements and photofragment imaging experiments are employed to investigate the dissociation energy of the Fe+(benzene) ion-molecule complex. Additional spectroscopy measurements determine the dissociation energy of Fe+(benzene)2. The dissociation energies for Fe+(benzene) determined from the threshold for the appearance of the Fe+ fragment (48.4 ± 0.2 kcal/mol) and photofragment imaging (≤49.3 ± 3.2 kcal/mol) agree nicely with each other and with the value determined previously by collision-induced dissociation (49.5 ± 2.9 kcal/mol), but they are lower than the values produced by computational chemistry at the density functional theory level using different functionals recommended for transition-metal chemistry. The threshold measurement for Fe+(benzene)2 (43.0 ± 0.2 kcal/mol) likewise agrees with the value (44.7 ± 3.8 kcal/mol) from previous collision-induced dissociation measurements.

Photodissociation Spectroscopy and Photofragment Imaging of the Fe+(Acetylene) Complex.

Tunable laser photodissociation spectroscopy in the 700-400 nm region and photofragment imaging experiments are employed to investigate the Fe+(acetylene) ion-molecule complex. At energies above a threshold at 679 nm, continuous dissociation is detected throughout the visible wavelength region, with regions of broad structure. Comparison to the spectrum predicted by time-dependent density functional theory (TD-DFT) indicates that the complex has a quartet ground state. The dissociation threshold for Fe+(acetylene) at 679 nm provides the dissociation energy on the quartet potential energy surface. Correction for the atomic quartet-sextet spin state energy difference provides an adiabatic dissociation energy of 36.8 ± 0.2 kcal/mol. Photofragment imaging of the Fe+ photoproduct produced at 603.5 nm produces significant kinetic energy release (KER). The photon energy and the maximum value of the KER provide an upper limit on the dissociation energy of D0 ≤ 34.6 ± 3.2 kcal/mol. The dissociation energies determined from the spectroscopy and photofragment imaging experiments agree nicely with the value determined previously by collision-induced dissociation (38.0 ± 2.6 kcal/mol). However, both values are significantly lower than those produced by computational chemistry at the DFT level using different functionals recommended for transition-metal chemistry.

Communication: Electronic transition of the l-C6 + cation at 417 nm.

A new electronic transition is reported for the linear C6 + cation with an origin at 416.8 nm. This spectrum can be compared to the matrix isolation spectra at lower energies reported previously by Fulara et al. [J. Chem. Phys. 123, 044305 (2005)], which assigned linear and cyclic isomers, and to the gas phase spectrum reported previously by Campbell and Dunk [Rev. Sci. Instrum. 90, 103101 (2019)], which detected the same cyclic-isomer spectrum reported by Fulara. Comparisons to electronically excited states and vibrations predicted by various forms of theory allow assignment of the spectrum to a new electronic state of linear C6 +. The spectrum consists of a strong origin band, two vibronic progression members at higher energy and four hot bands at lower energies. The hot bands provide the first gas phase information on ground state vibrational frequencies. The vibrational and electronic structure of C6 + provide a severe challenge to computational chemistry.

Photofragment Imaging of Carbon Cluster Cations: Explosive Ring Rupture.

Carbon cluster cations (Cn+) produced by laser vaporization are mass selected and photodissociated at 355 nm. Multiphoton dissociation of smaller ions leads to the elimination of neutral C3, as in previous work, whereas larger clusters exhibit more varied fragmentation channels. Photofragment velocity-map imaging detects significant kinetic energy release (KER) in the various n - 3 cation fragments. Small cations (n = 6 or 7) with linear structures produce moderate KER, whereas larger cations (n = 10, 11, 12, 15, or 20) having monocyclic ring structures produce much higher KER values. Such high KER values are unanticipated, as optical excitation should produce a wide distribution of internal energies. These carbon clusters have a surprising ability to absorb multiple photons of ultraviolet radiation, achieving a state of extreme excitation prior to dissociation. The remarkable nonstatistical distribution of energy is apparently influenced by the significant ring strain that can be released upon photodissociation.

Infrared spectroscopy of the protonated HCl dimer and trimer.

The protonated HCl dimer and trimer complexes were prepared by pulsed discharges in supersonic expansions of helium or argon doped with HCl and hydrogen. The ions were mass selected in a reflectron time-of-flight spectrometer and investigated with photodissociation spectroscopy in the IR and near-IR regions. Anharmonic vibrational frequencies were computed with VPT2 at the MP2/cc-pVTZ level of theory. The Cl-H stretching fundamentals and overtones were measured in addition to stretch-torsion combinations. VPT2 theory at this level confirms the proton-bound structure of the dimer complex and provides a reasonably good description of the anharmonic vibrations in this system. The trimer has a HCl-HClH+-ClH structure in which a central chloronium ion is solvated by two HCl molecules via hydrogen bonding. VPT2 reproduces anharmonic frequencies for this system, including several combinations involving core ion Cl-H stretches, but fails to describe the relative band intensities.

The Role of Tunneling in the Spectra of H5+ and D5+ up to 7300 cm-1.

The spectra for H5+ and D5+ are extended to cover the region between 4830 and 7300 cm-1. These spectra are obtained using mass-selected photodissociation spectroscopy. To understand the nature of the states that are accessed by the transitions in this and prior studies, we develop a four-dimensional model Hamiltonian. This Hamiltonian is expressed in terms of the two outer H2 stretches, the displacement of the shared proton from the center of mass of these two H2 groups, and the distance between the H2 groups. This choice is motivated by the large oscillator strength associated with the shared proton stretch and the fact that the spectral regions that have been probed correspond to zero, one, and two quanta of excitation in the H2 stretches. This model is analyzed using an adiabatic separation of the H2 stretches from the other two vibrations and includes the non-adiabatic couplings between H2 stretch states with the same total number of quanta of excitation in the H2 stretches. Based on the analysis of the energies and wave functions obtained from this model, we find that when there are one or more quanta of excitation in the H2 stretches the states come in pairs that reflect tunneling doublets. The states accessed by the transitions in the spectrum with the largest intensity are assigned to the members of the doublets with requisite symmetry that are localized on the lowest-energy adiabat for a given level of H2 excitation.