Dissociative Photodetachment Research Articles

Computational study of the post-transition state dynamics for the OH + CH3OH reaction probed by photodetachment of the CH3O-(H2O) anion.

Dissociative photodetachment dynamics simulations were conducted to study the CH3O-(H2O) → CH3O + H2O + e- reaction using classical molecular dynamics (MD) and ring-polymer molecular dynamics (RPMD) techniques on two newly formulated neutral potential energy surfaces (PES1 and PES2) by different research groups. While the dissociation dynamics exhibited similarities between classical MD and RPMD, there were noticeable differences in the fluctuation of probability densities for the internal modes due to nuclear quantum effects. Upon comparison of our findings with experimental data concerning the electron binding energy distribution and photofragment relative energy, it suggests that the potential energy landscapes of PES2 are reasonably precise. The time evolution of occupied vibrational states of the H2O photofragment is presented in this study.

Unraveling the decarboxylation dynamics of the fluorescein dianion with fragment action spectroscopy

The decarboxylation dynamics of the doubly deprotonated fluorescein dianion, Fl2-, are investigated by recording fragment action spectra for the anion, Fl-, and its decarboxylated analog, Fl-CO2-, using a new reflectron secondary mass spectrometer. The formation of the anion, Fl-, is directly investigated by photoelectron imaging. The Fl- and Fl-CO2- action spectra indicate that, for λ < 400nm, one-photon dissociative photodetachment, i.e., simultaneous decarboxylation and electron loss, competes with photodetachment, whereas for λ > 400nm, decarboxylation only proceeds following electron loss via a sequential two-photon process. The primary decarboxylation pathway is the ready loss of CO2 from the relatively short-lived intermediate excited state, Fl-[D1], which is formed by electron loss from the dianion via resonant tunneling through the repulsive Coloumb barrier associated with a high-lying excited dianion state, Fl2-[S2].

Photodetachment of Deprotonated R-Mandelic Acid: The Role of Proton Delocalization on the Radical Stability.

The photodetachment and stability of R-Mandelate, the deprotonated form of the R-Mandelic acid, was investigated by observing the neutral species issued from either simple photodetachment or dissociative photodetachment in a cold anions set-up. R-Mandalate has the possibility to form an intramolecular ionic hydrogen-bond between adjacent hydroxyl and carboxylate groups. The potential energy surface along the proton transfer (PT) coordinate between both groups (O- …H+ …- OCO) features a single local minima, with the proton localized on the O- group (OH…- OCO). However, the structure with the proton localized on the - OCO group (O- …HOCO) is also observed because it falls within the extremity of the vibrational wavefunction of the OH…- OCO isomer along the PT coordinate. The stability of the corresponding radicals, produced upon photodetachment, is strongly dependent on the position of the proton in the anion: the radicals produced from the OH…- OCO isomer decarboxylate without barrier, while the radicals produced from the O- …HOCO isomer are stable.

Probing the Exit Channel of the OH + CH3OH → H2O + CH3O Reaction by Photodetachment of CH3O-(H2O).

Transition state dynamics of bimolecular reactions can be probed by photodetachment of a precursor anion when the Franck-Condon region of the corresponding neutral potential energy surface is near a saddle point. In this study, photodetachment of anions at m/z = 49 enabled investigation of the exit channel of the OH + CH3OH → H2O + CH3O reaction using photoelectron-photofragment coincidence spectroscopy. High-level coupled-cluster calculations of the stationary points on the anion surface show that the methoxide-water cluster CH3O-(H2O) is the stable minimum on the anion surface. Photodetachment at a 3.20 eV photon energy leads to long-lived H2O(CH3O) complexes and H2O + CH3O products consistent with both direct dissociative photodetachment and resonance mediated processes on the neutral surface. The partitioning of total kinetic energy in the system indicates that water stretch and bend excitation is induced in dissociative photodetachment and evidence for long-lived complexes consistent with vibrational Feshbach resonances is reported.

On-the-Fly Ring-Polymer Molecular Dynamics Calculations of the Dissociative Photodetachment Process of the Oxalate Anion.

The dissociative photodetachment dynamics of the oxalate anion, C2O4H− + hν → CO2 + HOCO + e−, were theoretically studied using the on-the-fly path-integral and ring-polymer molecular dynamics methods, which can account for nuclear quantum effects at the density-functional theory level in order to compare with the recent experimental study using photoelectron–photofragment coincidence spectroscopy. To reduce computational time, the force acting on each bead of ring-polymer was approximately calculated from the first and second derivatives of the potential energy at the centroid position of the nuclei beads. We find that the calculated photoelectron spectrum qualitatively reproduces the experimental spectrum and that nuclear quantum effects are playing a role in determining spectral widths. The calculated coincidence spectrum is found to reasonably reproduce the experimental spectrum, indicating that a relatively large energy is partitioned into the relative kinetic energy between the CO2 and HOCO fragments. This is because photodetachment of the parent anion leads to Franck–Condon transition to the repulsive region of the neutral potential energy surface. We also find that the dissociation dynamics are slightly different between the two isomers of the C2O4H− anion with closed- and open-form structures.

Dissociative Photodetachment Dynamics of the OH-(C2H4) Anion Complex.

Photoelectron-photofragment coincidence (PPC) measurements on OH-(C2H4) anions at a photon energy of 3.20 eV revealed stable and dissociative photodetachment product channels, OH-C2H4 + e- and OH + C2H4 + e-, respectively. The main product channel observed was dissociation to the reactants (>67%), OH + C2H4 (v = 0, 1, 2) + e-, where vibrational excitation in the C-H stretching modes of the C2H4 photofragments corresponds to a minor channel. The low kinetic energy release (KER) of the dissociating fragments is consistent with weak repulsion between the OH + C2H4 reactants near the transition state as well as the partitioning of energy into rotation of the dissociation products. An impulsive model was used to account for rotational energy partitioning in the dissociative photodetachment (DPD) process and showed good agreement with the experimental results. The low KER of the dissociating fragments and the similarities in the photoelectron spectra between stable and dissociative events support a mechanism involving the van der Waals complex formed upon photodetachment of OH-(C2H4) as an intermediate in the dominant OH + C2H4 + e- dissociative channel.

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.

Dissociative photodetachment of H3O2-: a full-dimensional quantum dynamics study.

The transition state is a central concept of chemistry. Photoelectron-photofragment coincidence (PPC) spectroscopy has been proven as an attractive method to study the transition state dynamics. Within a state-of-the-art full-dimensional quantum mechanical model, the dissociative photodetachment dynamics of H3O2- is investigated on accurate anion and neutral potential energy surfaces. The calculated PPC spectrum of H3O2- agrees well with the experimental measurement. The dissociative product OH is exclusively populated on the ground vibrational state, implying the character of the spectator bond. In contrast, the product H2O is predominantly populated in the ground and fundamental states of the symmetric and antisymmetric stretching modes, which is caused by the strong coupling between the antisymmetric motion of the transferred H atom in the transient intermediate [H3O2]* and both stretching modes of the product H2O.

Theoretical study of the dissociative photodetachment dynamics of the hydrated superoxide anion cluster.

The dissociative photodetachment of the hydrated superoxide anion cluster, O2-·H2O + hν → O2 + H2O + e-, is theoretically investigated using path-integral and ring-polymer molecular dynamics simulation methods, which can account for nuclear quantum effects. Full-dimensional potential energy surfaces for the anionic and lowest two neutral states (triplet and singlet spin states) are constructed based on extensive density-functional theory calculations. The calculated photoelectron spectrum agrees well with the experimental spectra measured for different photodetachment laser wavelengths. The calculated photoelectron-photofragment kinetic energy correlation spectrum also agrees well with previous experimental measurements. The dissociation mechanisms, including available energy partitioning and the importance of nuclear quantum effects in photodetachment, are discussed in detail.

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.

Dissociative detachment of the fluoroformate anion.

Dissociative photodetachment of the FCO2- fluoroformate complex by intense laser pulses is studied using 3D coincidence fragment imaging. The main channels are found to be CO2 + F and FCO + O. Cleavage of the C-F bond is attributed to dissociation on the B[combining tilde]2A1 excited state of the neutral FCO2 radical with significant internal excitation of the molecular fragment, while reductive dissociation of the CO2 moiety is assigned to higher lying states. The measured dissociative ionization products of double-photodetachment are discussed and attributed to intense-laser ionization of dissociative photodetachment products.

Photoelectron-photofragment coincidence spectroscopy of the dissociative photodetachment of I2- at 258 and 266 nm

Photoelectron-photofragment coincidence (PPC) spectroscopy is used to examine the dissociative photodetachment (DPD) of at 266 and 258 nm in a kinematically complete manner. The resonance enhancement of predissociation in the DPD of is reported for the first time and a previously reported shift to a low KER channel at high photon energy is ascribed to vibrationally excited anions [K.E. Kautzman, P.E. Crider, D.E. Szpunar and D.M. Neumark, J. Phys. Chem. A 111 (49), 12795–12801 (2007)]. Photodetachment to the bound X and A states of results in stable , whereas excitation to a repulsive state results in dissociation of , forming two ground state I atoms. DPD occurs via multiple energetically accessible repulsive states, both directly and via predissociation of the bound state of . At 266 nm direct DPD and resonance enhanced predissociation dominate the DPD dynamics, whereas at 258 nm predissociation is less favoured and direct DPD shifts to preferentially occur via the state, particularly for vibrationally excited anions. Bound-continuum Franck–Condon factors are calculated to model the individual contributions to the dissociative photoelectron spectra from three energetically accessible repulsive states.

Resonance-Mediated Below-Threshold Delayed Photoemission and Non-Franck-Condon Photodissociation of Cold Oxyallyl Anions.

The photoexcitation of cold oxyallyl anions was studied below the adiabatic detachment threshold at a photon energy of 1.60 eV. Photodetachment was observed through two product channels, delayed electron emission from a long-lived anionic state and dissociative photodetachment via absorption of a second photon. The former produced stable neutral C3 H4 O, while the latter resulted in the concerted elimination of CO+C2 H4 products. The neutral oxyallyl singlet state has a barrier-free route to cyclopropanone as well as zwitterionic character with a large charge separation and dipole moment. The role of long-lived dipole-bound resonances built on the singlet state below the detachment threshold is discussed. These results provide one of the first observations of delayed photoemission in a small cold molecular radical anion, a consequence of the complex electronic structure of the neutral diradical, and provide an example of resonance-mediated control of the photodissociation processes.

Resonance‐Mediated Below‐Threshold Delayed Photoemission and Non‐Franck–Condon Photodissociation of Cold Oxyallyl Anions

AbstractThe photoexcitation of cold oxyallyl anions was studied below the adiabatic detachment threshold at a photon energy of 1.60 eV. Photodetachment was observed through two product channels, delayed electron emission from a long‐lived anionic state and dissociative photodetachment via absorption of a second photon. The former produced stable neutral C3H4O, while the latter resulted in the concerted elimination of CO+C2H4 products. The neutral oxyallyl singlet state has a barrier‐free route to cyclopropanone as well as zwitterionic character with a large charge separation and dipole moment. The role of long‐lived dipole‐bound resonances built on the singlet state below the detachment threshold is discussed. These results provide one of the first observations of delayed photoemission in a small cold molecular radical anion, a consequence of the complex electronic structure of the neutral diradical, and provide an example of resonance‐mediated control of the photodissociation processes.

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 and the oxalate anion C2O4H- at beam energies of 11 keV, 16 keV, and 21 keV.

Simultaneous 3D coincidence imaging of cationic, anionic, and neutral photo-fragments.

We present the design and simulations of a 3D coincidence imaging spectrometer for fast beam photofragmentation experiments. Coincidence detection of cationic, neutral, and anionic fragments involves spectrometer aberrations that are successfully corrected by an analytical model combined with exact numerical simulations. The spectrometer performance is experimentally demonstrated by characterization of four different channels of intense 800 nm pulse interaction with F2-: F- + F photodissociation, F + F dissociative photodetachment, F+ + F dissociative ionization, and F+ + F+ coulomb explosion. Improved measurement of F2- photodissociation with a 400 nm photon allows a better determination of the F2- anion dissociation energy, 1.256 ± 0.005 eV.

Effects of vibrational excitation on the F + H2O → HF + OH reaction: dissociative photodetachment of overtone-excited [F-H-OH

The reaction F + H2O → HF + OH is a four-atom system that provides an important benchmark for reaction dynamics. Hydrogen atom transfer at the transition state for this reaction is expected to exhibit a strong dependence on reactant vibrational excitation. In the present study, the vibrational effects are examined by photodetachment of vibrationally excited F-(H2O) precursor anions using photoelectron-photofragment coincidence (PPC) spectroscopy and compared with full six-dimensional quantum dynamical calculations on ab initio potential energy surfaces. Prior to photodetachment at hνUV = 4.80 eV, the overtone of the ionic hydrogen bond mode in the precursor F-(H2O), 2νIHB at 2885 cm-1, was excited using a tunable IR laser. Experiment and theory show that vibrational energy in the anion can be effectively carried away by the photoelectron upon a Franck-Condon photodetachment, and also show evidence for an increase of branching into the F + H2O reactant channel. The experimental results suggest a greater role for product rotational excitation than theory. Improved potential energy surfaces and longer wavepacket propagation times would be helpful to further examine the nature of the discrepancy.

Photoelectron-photofragment coincidence studies of the tert-butoxide anion (CH3)3CO((-)), the carbanion isomer (CH3)2CH2COH((-)), and corresponding radicals.

A study of the photodetachment and dissociative photodetachment (DPD) of the C(4)H(9)O(-) isomers tert-butoxide, (CH(3))(3)CO(-), and the α-hydroxy carbanion (CH(3))(2)C(CH(2))OH(-) is reported. Photoelectron-photofragment coincidence spectroscopy was used to study these anions at 387, 537, and 600 nm. Supported by CBS-QB3 ab initio calculations, the product mass and translational energy distributions were found to be consistent with dissociation of either highly excited (CH3)(3)CO radicals or (CH(3))(2)C(CH2)OH alkylhydroxy radicals. Vibrationally resolved photoelectron spectra of stable radicals at 537 and 600 nm in conjunction with Franck-Condon simulations were used to assign the dominant channel to tert-butoxide ((CH(3)3)CO(-)) anions thermalized to a vibrational temperature of 550 K. DPD is assigned to highly vibrationally excited radicals produced by photodetachment of unrelaxed tert-butoxide products formed at an effective source temperature of 1400 K. The higher energy carbanion was found to be a minor channel and was not observed to dissociate. Calculated energetics for photodetachment and DPD of (CH(3))(3)CO(-) and (CH(3))(2)C(CH(2))OH(-) are discussed and compared with the experimental results.