Photoelectron photofragment coincidence spectroscopy of aromatic carboxylates: benzoate and p-coumarate.

Photoelectron-photofragment coincidence spectroscopy was used to study the dissociation dynamics of the conjugate bases of benzoic acid and p-coumaric acid. Upon photodetachment at 266 nm (4.66 eV) both aromatic carboxylates undergo decarboxylation, as well as the formation of stable carboxyl radicals. The key energetics are computed using high-level electronic structure methods. The dissociation dynamics of benzoate were dominated by a two-body DPD channel resulting in CO2 + C6H5 + e-, with a very small amount of stable C6H5CO2 showing that the radical ground state is stable and the excited states are dissociative. For p-coumarate (p-CA-) the dominant channel is photodetachment resulting in a stable radical and a photoelectron with electron kinetic energy (eKE) <2 eV. We also observed a minor two-body dissociative photodetachment (DPD) channel resulting in CO2 + HOC6H4CHCH + e-, characterized by eKE <0.8 eV. Evidence was also found for a three-body ionic photodissociation channel producing HOC6H5 + HCC- + CO2. The ion beam contained both the phenolate and carboxylate isomers of p-CA-, but DPD only occurred from the carboxylate form. For both species DPD is seen from the first and second excited states of the radical, where vibrational excitation is required for decarboxylation from the first excited radical state.

Photoelectron photofragment coincidence spectroscopy of carboxylates.

Photoelectron-photofragment coincidence (PPC) spectroscopy is a powerful technique for studying the decarboxylation dynamics of carboxyl radicals. Measurement of photoelectron and photofragment kinetic energies in coincidence provides a kinematically complete measure of the dissociative photodetachment (DPD) dynamics of carboxylate anions. PPC spectroscopy studies of methanoate, ethanoate, propanoate, 2-butenoate, benzoate, p-coumarate and the oxalate monoanion are reviewed. All of the systems studied undergo decarboxylation via a two-body DPD channel i.e., driven by the thermodynamic stability of CO2. Additionally, decarboxylation is observed via a three-body ionic photodissociation channel for p-coumarate. In some cases photodetachment also results in a stable carboxyl radical (RCO2). The branching ratio for DPD, the threshold detachment energy and the peak of the kinetic energy release spectrum are compared for different carboxylates, as a probe of the character of the potential energy landscape in the Franck-Condon region.

Photoelectron-photofragment coincidence spectroscopy of the mixed trihalides.

Photoelectron-photofragment coincidence (PPC) spectroscopy is used to study the photodetachment, photodissociation, and dissociative photodetachment (DPD) of I2Br-, IBr2 -, I2Cl-, and ICl2 - at 266 nm. The mixed trihalides are asymmetric analogs of the well-studied I3 - anion, with distinguishable dissociation asymptotes and the potential for selective bond breaking. The high beam energy PPC spectrometer used in this study couples an electrospray ionization source, a hexapole accumulation ion trap, and a linear accelerator to produce a 21 keV beam of a particular trihalide. Total, stable, and dissociative photoelectron spectra have been recorded for all the anions, except ICl2 - that does not photodetach at 266 nm. A bound ground state (X) is observed for all the anions, and a dissociative first excited (A) state is also seen for I2Br- and I2Cl- at low electron kinetic energies (eKE). A 258 nm photoelectron spectrum recorded for I2Br- and I2Cl- rules out autodetachment of a dipole-bound state as the origin of the low eKE feature. The threshold detachment energy (TDE) of I2X- to the X state of the radical is similar to I3 -, whereas the TDE to the radical A state increases with substitution of iodine for a lighter halogen. Two-body DPD is observed for I2Br- and I2Cl-, resulting in IBr/ICl + I + e-. For IBr2 - and ICl2 -, the charge symmetric three-body photodissociation of [Br-I-Br]- and [Cl-I-Cl]- is seen yielding Br + Br and Br + Br*, and Cl + Cl and Cl + Cl* neutral fragments. Evidence for the minimum energy anion structure is observed in all cases, where the iodine atom is located at the center of the trihalide.

Dissociative photodetachment dynamics of the oxalate monoanion.

The dissociative photodetachment (DPD) dynamics of the oxalate monoanion are studied using photoelectron-photofragment coincidence (PPC) spectroscopy. Following photodetachment of C2O4H- at 4.66 eV HOCO + CO2 products are observed, indicating the facile decarboxylation of the radical driven by the thermodynamic stability of CO2. No evidence is seen for photodetachment to stable C2O4H or ionic photodissociation to produce HOCO-. Calculations indicate the stabilizing presence of an intramolecular hydrogen bond in the anion via the formation of a strained five-membered ring. No intramolecular hydrogen bond is predicted in the radical due to the lower charge density on the oxygen atom. The PPC spectrum is consistent with a single direct two-body DPD channel that results in fragments of similar mass and is characterized by a large kinetic energy release (KER) and a broad photoelectron spectrum. The large KER is indicative of substantial repulsion in the radical following photodetachment. The form of the photoelectron spectrum is dominated by the bound to continuum Franck-Condon factors (BCFCF) and is suggestive of photodetachment to a repulsive potential energy surface. A lower bound for the electron affinity of C2O4H is reported as 4 eV. BCFCF calculations allow an approximate functional form of the repulsive surface along the C-C stretch coordinate to be extracted from the experimental photoelectron spectrum. PPC spectroscopy of the deuterated analogue (C2O4D-), at higher anion beam energies is used to increase the detectability of any possible D atom products, but none are observed.

Photoelectron-photofragment coincidence studies of I3- using an electrospray ionization source and a linear accelerator.

Photoelectron-photofragment coincidence (PPC) spectroscopy is used to examine the dissociative photodetachment (DPD) of I3-. The high beam energy PPC spectrometer for complex anions couples an electrospray ionization source, a hexapole accumulation ion trap and a linear accelerator to produce fast beams of I3- (M = 381 amu) anions, the heaviest system studied to date. Following photodetachment, the photoelectron and up to three photofragments are recorded in coincidence yielding a kinematically complete picture of the DPD dynamics at beam energies of 11 keV and 21 keV. Photodetachment leads to the production of stable I3, two-body DPD, as well as evidence for two- and three-body photodissociation. DPD is found to occur predominantly via the first excited A state, with some contributions from highly excited vibrational levels in the neutral ground state. With the ions thermalized to 298 K in the hexapole trap, there are significant contributions from vibrational hot bands. Three-body photodissociation at 4.66 eV is found to occur preferentially via a charge-symmetric process to form I + I- + I. In the future this method will be applied to other polyatomic systems with a large molecular mass, including multiply charged anions and complex clusters, in concert with a cryogenically cooled hexapole trap to reduce thermal effects.

A high beam energy photoelectron-photofragment coincidence spectrometer for complex anions.

A new high beam energy photoelectron-photofragment coincidence (PPC) spectrometer is described that allows acceleration of heavy anions (>100 amu) to energies in the tens of keV using a linear accelerator (LINAC). High beam energies result in more efficient detection of the neutral photofragments produced via dissociative photodetachment (DPD) of the parent anion and increase the mass range that can be studied with PPC spectroscopy. The novel experimental setup couples an electrospray ionization (ESI) source and a hexapole accumulation trap with a 10-stage LINAC to give a kinematically complete measurement of the dissociation dynamics for heavier anions. ESI dramatically increases the range of anions that can be studied by PPC spectroscopy to include multiply charged anions and larger, more complex molecular ions important in biological, atmospheric, and combustion processes. A radiofrequency buffer-gas-cooled hexapole trap is used to accumulate sufficient ion density for single-shot coincidence measurements and thermalize the anions to room temperature. The photoelectron and up to three neutral fragments resulting from DPD are recorded in coincidence using time and position sensitive detectors. This novel experimental setup is characterized by studying the photodetachment of I-, and the DPD of I 2 - and the oxalate anion C2O4H- at beam energies of 11 keV, 16 keV, and 21 keV.

An ion mobility mass spectrometer for investigating photoisomerization and photodissociation of molecular ions.

An ion mobility mass spectrometry apparatus for investigating the photoisomerization and photodissociation of electrosprayed molecular ions in the gas phase is described. The device consists of a drift tube mobility spectrometer, with access for a laser beam that intercepts the drifting ion packet either coaxially or transversely, followed by a quadrupole mass filter. An ion gate halfway along the drift region allows the instrument to be used as a tandem ion mobility spectrometer, enabling mobility selection of ions prior to irradiation, with the photoisomer ions being separated over the second half of the drift tube. The utility of the device is illustrated with photoisomerization and photodissociation action spectra of carbocyanine molecular cations. The mobility resolution of the device for singly charged ions is typically 80 and it has a mass range of 100-440 Da, with the lower limit determined by the drive frequency for the ion funnels, and the upper limit by the quadrupole mass filter.

Changing the shape of molecular ions: photoisomerization action spectroscopy in the gas phase.

A new approach for studying the photoisomerization of molecular ions in the gas phase is described. Packets of molecular ions are injected into a drift tube filled with helium buffer gas, where they are irradiated with tunable laser light. Photoisomerization changes the ions' cross section for collisions with helium atoms so that they arrive at the ion detector slightly earlier or later than the parent ions. By monitoring the photo-isomer peak as a function of laser wavelength one can record an action spectrum that is related to the ions' absorption spectrum modulated by the photoisomerization probability. The approach is demonstrated using the polymethine dye HITC (1,3,3,1',3',3'-hexamethylindotricarbocyanine). The data show that both trans and cis forms of HITC(+) exist in the gas phase with trans→cis photoisomerization predominating over the 550-710 nm range and cis→trans photoisomerization occurring over the 735-770 nm range. The gas-phase photoisomerization action spectrum is comparable to the absorption spectra of trans HITC and cis HTIC in the condensed phase, but with the absorption peaks shifted to shorter wavelength. The gas-phase photoisomerization action spectrum of the (HITC)2(2+) dication dimer is also reported. (HITC)2(2+) cations photoisomerize over the 550-770 nm range to form more compact structures.

Effects of alkyl substitution on the energetics of enolate anions and radicals.

The photoelectron spectra of the structural isomers of the three- and four-carbon enolate anions, n-C3H5O(-), i-C3H5O(-), n-C4H7O(-), s-C4H7O(-), and i-C4H7O(-) have been measured at 355 nm. Both the X(2A' ') ground and A(2A') first excited states of the corresponding radicals were accessed from the X(1A') ground state of the enolate anions. The separation energies of the ground and first excited states (T0) were determined: T0[(E)-n-C3H5O] = 1.19 +/- 0.02 eV, T0[(Z)-n-C3H5O] = 0.99 +/- 0.02 eV, T0[i-C3H5O] = 1.01 +/- 0.02 eV, T0[n-C4H7O] = 1.19 +/- 0.02 eV, T0[(2,3)-s-C4H7O] = 1.25 +/- 0.02 eV, T0[(1,2)-s-C4H7O] = 0.98 +/- 0.02 eV, and T0[i-C4H7O] = 1.36 +/- 0.02 eV. The effects of alkyl substitution on the vibronic structure and energetics previously observed in the vinoxy radical are discussed. The X(1A')-X(2A' ') relative stability is strongly influenced by substitution whereas the X(1A')-A(2A') relative stability remains nearly constant for all of the observed structural isomers. Alkyl substitution at the carbonyl carbon affects vibronic structure more profoundly than the energetics, while the converse is observed upon alkyl substitution at the alpha carbon.

Coincidence spectroscopy.

The application of coincidence techniques to the study of the reaction dynamics of isolated molecules is reviewed. Coincidence spectroscopy is a powerful approach for carrying out a number of measurements. At its most basic level, coincidence techniques can identify the source of a specific signal, as in the well-known photoelectron-photoion coincidence approach used for several years. By carrying out coincidence experiments in an increasingly differential manner, correlated energy and angular distributions of reaction products may be recorded. Completely energy- and angle-resolved measurements of photoelectrons and ionic or neutral products can reveal molecular-frame photoelectron and photofragment angular distributions and aid in the characterization of dissociative states of molecules and ions. Recent work in this area is reviewed, including examples from studies of dissociative photodetachment, dissociative photoionization, time-resolved studies of dissociative photoionization, and three-body dissociation processes.

Transition state dynamics of the OH + H2O hydrogen exchange reaction studied by dissociative photodetachment of H3O2-.

Dynamics in the transition state region of the bimolecular OH + H2O-->H2O + OH hydrogen exchange reaction have been studied by photoelectron-photofragment coincidence spectroscopy of the H3O2- negative ion and its deuterated analog D3O2-. The data reveal vibrationally resolved product translational energy distributions. The total translational energy distribution shows a vibrational progression indicating excitation of the antisymmetric stretch of the water product. Electronic structure calculations at the QCISD level of theory support this analysis. Examination of the translational energy release between the neutral products reveals a dependence on the product vibrational state. These data should provide a critical test of ab initio potential energy surfaces and dynamics calculations.

Femtosecond time-resolved photoelectron angular distributions probed during photodissociation of NO2.

Femtosecond time-resolved photoelectron angular distributions (PADs) are measured for the first time in the molecular frame of a dissociating molecule. Various stages of the dissociation process, NO2-->NO(C Pi)+O(P), are probed using ionization of the NO(C Pi) fragment to NO+(X Sigma(+)). The PADs evolve from forward-backward asymmetric with respect to the dissociation axis at short time delays ( < or =500 fs) to symmetric at long time delays (> or = 1 ps). Changes in the PADs directly reflect the time-dependent separation and reorientation of the dissociating photofragments.