Threshold Photoelectron Spectra Research Articles

A Study of H2O2 with Threshold Photoelectron Spectroscopy (TPES) and Electronic Structure Calculations: Redetermination of the First Adiabatic Ionization Energy (AIE).

In this work, hydrogen peroxide has been studied with threshold photoelectron (TPE) spectroscopy and photoelectron (PE) spectroscopy. The TPE spectrum has been recorded in the 10.0-21.0 eV ionization energy region, and the PE spectrum has been recorded at 21.22 eV photon energy. Five bands have been observed which have been assigned on the basis of UCCSD(T)-F12/VQZ-F12 and IP-EOM CCSD calculations. Vibrational structure has only been resolved in the TPE spectrum of the first band, associated with the X̃(2)Bg H2O2(+) ← X̃(1)A H2O2 ionization, on its low energy side. This structure is assigned with the help of harmonic Franck-Condon factor calculations that use the UCCSD(T)-F12a/VQZ-F12 computed adiabatic ionization energy (AIE), and UCCSD(T)-F12a/VQZ-F12 computed equilibrium geometric parameters and harmonic vibrational frequencies for the H2O2 X̃(1)A state and the H2O2(+) X̃(2)Bg state. These calculations show that the main vibrational structure on the leading edge of the first TPE band is in the O-O stretching mode (ω3) and the HOOH deformation mode (ω4), and comparison of the simulated spectrum to the experimental spectrum gives the first AIE of H2O2 as (10.685 ± 0.005) eV and ω4 = (850 ± 30) and ω3 = (1340 ± 30) cm(-1) in the X̃(2)Bg state of H2O2(+). Contributions from ionization of vibrationally excited levels in the torsion mode have been identified in the TPE spectrum of the first band and the need for a vibrationally resolved TPE spectrum from vibrationally cooled molecules, as well as higher level Franck-Condon factors than performed in this work, is emphasized.

High-Resolution Threshold Photoelectron Spectroscopy by Vacuum Ultraviolet Laser Velocity-Map-Imaging Method

We have obtained the high-resolution threshold photoelectron (TPE) spectra of chlorobenzene C6H5Cl (X1A1), propargyl radical C3H3 (X2B1), and allyl radical C3H5 (X2A1) by employing the vacuum ultraviolet (VUV) laser velocity-map-imaging-TPE (VUV-VMI-TPE) method. The photoelectron energy resolution of 1–2 cm−1 observed for the VUV-VMI-TPE method is comparable to that achieved in VUV laser pulsed-field ionization-photoelectron (VUV-PFI-PE) measurements. Similar to VUV-PFI-PE measurements, the energy resolutions for VUV-VMI-photoelectron (VUV-VMI-PE) and VUV-VMI-TPE measurements are found to depend on the dc electric field F in V/cm used at the photoionization region for electron extraction. The decrease of the ionization thresholds of C6H5Cl and C3H3 observed as a function of F shows that the Stark shift correction for VUV-VMI-TPE measurements is governed by the formula −3.1F in cm−1, which is half of the classical prediction of −6.1F in cm−1. We have also measured the VUV-VMI-PE spectra of C6H5Cl and C3H5 ...

Pyrolysis of 3-Methoxypyridine. Detection and Characterization of the Pyrrolyl Radical by Threshold Photoelectron Spectroscopy

Pyrolysis of 3-methoxypyridine in a heated pyrolysis reactor was found to be an efficient way to generate the pyrrolyl radical, c-C4H4N, in the gas phase. The threshold photoelectron (TPE) spectrum of this radical was recorded using vacuum ultraviolet synchrotron radiation. The spectrum revealed a singlet ground state at 9.11 ± 0.02 eV (X̃(+1)A) and an excited triplet state (ã(+3)A) at 9.43 ± 0.05 eV. Vibrational structure was observed for both cationic states and could be assigned to ring deformation modes. Furthermore, (E)- and (Z)-1-cyanoallyl radicals were found to contribute to the TPE spectrum below 8.9 eV. In addition, we have identified two parallel decomposition channels of the pyrrolyl radical, yielding either hydrogen cyanide and propargyl radical or acetylene and cyanomethyl radical. The reaction energy profiles have also been calculated for these reactions. In addition, the dissociative photoionization of the precursor 3-methoxypyridine is reported.

The threshold photoelectron spectrum of cyanovinylacetylene leads to an upward revision of the ionization energy

Cyanovinylacetylene C5H3N was investigated by threshold photoelectron spectroscopy. The ionization energy (IE) was determined to be 10.04eV. This value constitutes an upward revision of the earlier value of 9.33eV. For both stereoisomers (trans and cis) computations predict very similar IEs and spectra. At 11.08eV and 11.17eV excited cationic states are observed. For the precursor 3-bromopyridine an IE of 9.34eV was obtained. The appearance energy AE0K (3-bromopyridine, 3-pyridyl+) was determined to be 11.71eV and a bond dissociation energy of the CBr bond in the 3-bromopyridine cation of 229kJmol−1 was derived.

The ionisation energy of cyclopentadienone: a photoelectron–photoion coincidence study

Imaging photoelectron photoion coincidence (iPEPICO) spectra of cyclopentadienone (C5H4=O and C5D4=O) have been measured at the Swiss Light Source Synchrotron (Paul Scherrer Institute, Villigen, Switzerland) at the Vacuum Ultraviolet (VUV) Beamline. Complementary to the photoelectron spectra, photoionisation efficiency curves were measured with tunable VUV radiation at the Chemical Dynamics Beamline at the Advanced Light Source Synchrotron (Lawrence Berkeley National Laboratory, Berkeley, CA, USA). For both experiments, molecular beams diluted in argon and helium were generated from the vacuum flash pyrolysis of o-phenylene sulphite in a resistively heated microtubular SiC flow reactor. The Franck–Condon profiles and ionisation energies were calculated at the CCSD(T) level of theory, and are in excellent agreement with the observed iPEPICO spectra. The ionisation energies of both cyclopentadienone-d0, IE(C5H4=O), and cyclopentadienone-d4, IE(C5D4=O), were observed to be the same: 9.41 ± 0.01 eV. The mass-selected threshold photoelectron spectrum (ms-TPES) of cyclopentadienone reveals that the C=C stretch in the ground state of the cation is excited upon ionisation, supporting computational evidence that the ground state of the cation is 2A2, and is in agreement with previous studies. However, the previously reported ionisation potential has been improved considerably in this work. In addition, since o-benzoquinone (o-O=C6H4=O and o-O=C6D4=O) is also produced in this process, its ms-TPES has been recorded. From the iPEPICO and photoionisation efficiency spectra, we infer an adiabatic ionisation energy of IE(o-O=C6H4=O) = 9.3 ± 0.1 eV, but the rather structureless spectrum indicates a strong change in geometry upon ionisation making this value less reliable.

Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO(+) and vibrational resolution in NCO(.).

The threshold photoelectron spectra (TPES) of two unstable nitrogen-containing species, HNCO and NCO, were recorded utilizing vacuum ultraviolet synchrotron radiation. Both are intermediates in combustion processes and play a role in the removal of nitrogen oxides from exhaust gases. The rovibronic structure of the first band in the TPES of HNCO(+) was analyzed within the framework of an orbital ionization model, and the resolved structure of the origin band was assigned to ΔK subbands. An ionization energy of 11.602 ± 0.005 eV was determined and the vibrational structure of the cationic ground state was analyzed by a Franck-Condon fit. Low lying electronically excited states of HNCO(+) were also observed. In a second series of experiments, the NCO radical was generated by flash pyrolysis from chlorine isocyanate. The ionization energy to the X(+) (3)Σ(-) ground state was determined to be 11.76 ± 0.02 eV, while for the a(+) (1)Δ state, a value of 12.93 ± 0.02 eV was obtained. Vibrational structure was observed for both states, and bands were assigned by Franck-Condon simulations.

Threshold Photoelectron Spectra of Combustion Relevant C4H5 and C4H7 Isomers.

Threshold photoelectron spectra of combustion relevant C4H5 isomers, 2-butyn-1-yl and 1-butyn-3-yl, and C4H7 isomers, 1-methylallyl and 2-methylallyl, have been recorded using vacuum ultraviolet synchrotron radiation. Adiabatic ionization energies (IEad) have been determined by assigning spectroscopic transitions in mass-selected threshold photoelectron spectra aided by Franck-Condon simulations. The following values were obtained: (7.97 ± 0.02) eV (1-butyn-3-yl), (7.94 ± 0.02) eV (2-butyn-1-yl), (7.48 ± 0.01) eV (1-E-methylallyl), (7.59 ± 0.01) eV (1-Z-methylallyl), and (7.88 ± 0.01) eV (2-methylallyl). Good agreement with CBS-QB3 calculations and simulations could be achieved.

Threshold photoelectron spectrum of the benzyl radical

We measure threshold photoelectron spectra of the benzyl radical, which show transitions to at least three electronic states of the benzylium cation: 1A1, 3B2, and 1B2, with possible contributions from transitions to 3A1. The main features in the vibrationally resolved threshold photoelectron spectrum between 7.1 and 10.5 eV are assigned with the aid of Franck–Condon simulations to these four electronic states of benzylium. We measure the adiabatic ionisation energy of the benzyl radical to be 7.252(5) eV and observe a well-resolved vibrational progression in the lowest triplet state, 3B2, from which we obtain a measured singlet–triplet splitting of 1.928(7) eV in benzylium.

Photoionization spectroscopy of CH3C3N in the vacuum-ultraviolet range

Using vacuum-ultraviolet (VUV) synchrotron radiation, threshold and dissociative photoionization of cyanopropyne (CH3C3N) in the gas phase have been studied from 86000cm−1 up to 180000cm−1 by recording Threshold-PhotoElectron Spectrum (TPES) and PhotoIon Yield (PIY). Ionization energies of the four lowest electronic states X̃+2E,Ã+2A1,B̃+2E and C̃+ of CH3C3N+ are derived from the TPES with a better accuracy than previously reported. The adiabatic ionization potential of CH3C3N is measured as 86872±20 cm−1. A description of the vibrational structure of these states is proposed leading to the first determination of the vibrational frequencies for most modes. The vibrational assignments of the X̃+ state are supported by density functional theory calculations. In addition, dissociative photoionization spectra have been recorded for several cationic fragments in the range 12–15.5eV (96790–125000cm−1) and they bring new information on the photophysics of CH3C3N+. Threshold energies for the cationic dissociative channels leading to CH2C3N+, CHC3N+, HC3H+, HCNH+ and CH3+ have been measured for the first time and are compared with quantum chemical calculations.

Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer.

We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME - h6)n and (DME - d6)n n = 1 and 2, in the 9-14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C-H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH3OHCH3 (+) by the loss of CH2OCH3 with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME - h6)2 and deuterated (DME - d6)2, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME - d6 monomer.

The vacuum-ultraviolet photoelectron spectra of CH2F2 and CH2Cl2 revisited

The threshold photoelectron spectrum (TPES) of difluoromethane and dichloromethane has been recorded at the Swiss Light Source with a resolution of 2meV or 16cm−1. Electronic and vibronic transitions are simulated and assigned with the help of Franck–Condon (FC) calculations based on coupled cluster electronic structure calculations for the equilibrium geometries and harmonic vibrational frequencies of the neutrals, and of the ground and excited electronic states of the cations. Notwithstanding a high-resolution pulsed-field ionisation study on CH2F2 (Forysinski et al., 2010) in which a number of transitions to the X∼+ state have been recorded with unprecedented accuracy, we report the first complete vibrationally resolved overview of the low-lying electronic states of CH2X2+, X=F or Cl. Hydrogen atom loss from CH2F2+ occurs at low energy, making the ground state rather anharmonic and interpretation of the X∼+ band challenging in the harmonic approximation. By Franck–Condon fits, the adiabatic ionisation energies to the A∼+2B2, C∼+2A2 and D∼+2B2 states have been determined as 14.3±0.1, 15.57±0.01 and 18.0±0.1eV, respectively. The first band in the CH2Cl2 TPES is complex for a different reason, as it is the result of two overlapping ionic states, X∼+2B2 and A∼+2B1, with derived ionisation energies of 11.0±0.2 and 11.317±0.006eV, and dominated by an extended progression in the CCl2 bend (in X∼+) and a short progression in the CCl2 symmetric stretch (in A∼+), respectively. Furthermore, even though Koopmans’ approximation holds for the vertical ionisations, the X∼+ state of CH2Cl2+ is stabilized by geometry relaxation and corresponds to ionisation from the (HOMO−1) orbital. That is, the first two vertical ionisation energies are in the same order as the negative of the orbital energies of the highest occupied orbitals, but the adiabatic ionisation energy corresponding to electron removal from the (HOMO−1) is lower than the adiabatic ionisation energy corresponding to electron removal from the HOMO. The second band in the spectrum could be analysed to identify the vibrational progressions and determine adiabatic ionisation energies of 12.15 and 12.25eV for the B∼+2A1 and C∼+2A2 states. A comparison of the assignment of electronic states with the literature is made difficult by the fact that the B1 and B2 irreducible representations in C2v symmetry depend on the principal plane, i.e. whether the CX2 moiety is in the xz or the yz plane, which is often undefined in older papers.

Dissociative photoionization of quinoline and isoquinoline.

Two nitrogen-containing polycyclic aromatic hydrocarbon isomers of C9H7N composition, quinoline, and isoquinoline have been studied by imaging photoelectron photoion coincidence spectroscopy at the VUV beamline of the Swiss Light Source. High resolution threshold photoelectron spectra have been recorded and are interpreted applying a Franck-Condon model. Dissociative ionization mass spectra as a function of the parent ion internal energy are analyzed with the use of breakdown diagrams. HCN loss and H loss are the dominant dissociation paths for both C9H7N(•+) isomers at photon energies below 15.5 eV. Computed C9H7N(•+) potential energy surfaces suggest that the lowest energy path leading to HCN-loss yields the benzocyclobutadiene cation. A statistical model is used to fit the breakdown diagram and-to account for the kinetic shift-the time-of-flight mass spectra that reveal the dissociation rates. We have derived appearance energies of 11.9 ± 0.1 (HCN loss) and 12.0 ± 0.1 (H loss), as well as 11.6 ± 0.2 (HCN loss) and 12.1 ± 0.2 (H loss) eV, for the dissociative ionization of quinoline and isoquinoline, respectively. The results are compared to a recent study on the dissociative ionization of naphthalene. Implications for the formation and destruction of nitrogenated PAHs in the interstellar medium and in Titan's atmosphere are highlighted.

Theoretical and Experimental Photoelectron Spectroscopy Characterization of the Ground State of Thymine Cation.

We report on the vibronic structure of the ground state X̃(2)A″ of the thymine cation, which has been measured using a threshold photoelectron photoion coincidence technique and vacuum ultraviolet synchrotron radiation. The threshold photoelectron spectrum, recorded over ∼0.7 eV above the ionization potential (i.e., covering the whole ground state of the cation) shows rich vibrational structure that has been assigned with the help of calculated anharmonic modes of the ground electronic cation state at the PBE0/aug-cc-pVDZ level of theory. The adiabatic ionization energy has been experimentally determined as AIE = 8.913 ± 0.005 eV, in very good agreement with previous high resolution results. The corresponding theoretical value of AIE = 8.917 eV has been calculated in this work with the explicitly correlated method/basis set (R)CCSD(T)-F12/cc-pVTZ-F12, which validates the theoretical approach and benchmarks its accuracy for future studies of medium-sized biological molecules.

Assignment of high-lying bending mode levels in the threshold photoelectron spectrum of NH2: a comparison between pyrolysis and fluorine-atom abstraction radical sources.

In this manuscript we present threshold photoelectron spectra (TPES) of the amidogen radical, NH2, recorded at two vacuum ultraviolet synchrotron radiation beamlines, the DESIRS beamline of Synchrotron SOLEIL and the VUV beamline of the Swiss Light Source (SLS). Amidogen radicals were generated by two different methods, (a) H-atom abstraction of ammonia in a fluorine microwave discharge flow tube and (b) flash pyrolysis of methylhydrazine and diphenylmethylamine. Due to the large geometry change upon photoionization from the bent neutral molecule NH2 (X[combining tilde] (2)B1) to the quasi-linear cation NH2(+) (X[combining tilde] (3)B1), significant activity in the bending vibration υ2(+) of NH2(+) (X[combining tilde] (3)B1) is observed in the TPES. Transitions into a large number of υ2(+), Ka(+) levels of the cation are resolved.

Decomposition of diazomeldrum's acid: a threshold photoelectron spectroscopy study.

Derivatives of meldrum's acid are known precursors for a number of reactive intermediates. Therefore, we investigate diazomeldrum's acid (DMA) and its pyrolysis products by photoionization using vacuum ultraviolet (VUV) synchrotron radiation. The threshold photoelectron spectrum of DMA yields an ionization energy (IE) of 9.68 eV. Several channels for dissociative photoionization are observed. The first one is associated with loss of CH3, leading to a daughter ion with m/z = 155. Its appearance energy AE0K was determined to be 10.65 eV by fitting the experimental data using statistical theory. A second parallel channel leads to m/z = 69, corresponding to N2CHCO, with an AE0K of 10.72 eV. Several other channels open up at higher energy, among them the formation of acetone cation, a channel expected to be the result of a Wolff-rearrangement (WR) in the cation. When diazomeldrum's acid is heated in a pyrolysis reactor, three thermal decomposition pathways are observed. The major one is well-known and yields acetone, N2 and CO as consequence of the WR. However, two further channels were identified: The formation of 2-diazoethenone, NNCCO, together with acetone and CO2 as the second channel and E-formylketene (OCCHCHCO), propyne, N2 and O2 as a third one. 2-Diazoethenone and E-formylketene were identified based on their threshold photoelectron spectra and accurate ionization energies could be determined. Ionization energies for several isomers of both molecules were also computed. One of the key findings of this study is that acetone is observed upon decomposition of DMA in the neutral as well as in the ion and both point to a Wolff rearrangement to occur. However, the ion is subject to other decomposition channels favored at lower internal energies.

Vacuum ultraviolet photoionization study of gas phase vitamins A and B1 using aerosol thermodesorption and synchrotron radiation.

Gas-phase studies of biomolecules are often difficult to initiate because of the thermolability of these systems. Such studies are nevertheless important to determine fundamental intrinsic properties of the molecules. Here we present the valence shell photoionization of gas-phase vitamins A and B1 close to their ionization threshold. The study was performed by means of an aerosol thermodesorption source coupled to an electron/ion coincidence spectrometer and synchrotron radiation (SOLEIL facility, France). Ion yield curves were recorded for both molecules over a few electronvolt energy range and the threshold photoelectron spectrum was also obtained for vitamin A. Some fundamental properties were extracted for both ions such as adiabatic and the three first vertical ionization energies of retinol (IEad = 6.8 ± 0.2 eV and IEvert = 7.4, 8.3, and 9.2 eV) and dissociation appearance energies for the main fragment ions of vitamin B1. Analysis of the data was supported by ab initio calculations which show a very good agreement with the experimental observations.

Dissociative photoionization and threshold photoelectron spectra of polycyclic aromatic hydrocarbon fragments: an imaging photoelectron photoion coincidence (iPEPICO) study of four substituted benzene radical cations.

Four molecules were investigated by imaging photoelectron photoion coincidence (iPEPICO) spectroscopy: 1-propynylbenzene, indene, ethynylbenzene, and benzocyclobutene. Their threshold photoelectron spectrum was obtained and electronic transitions were assigned by OVGF (outer valence Green's function) calculations. Vibrational progressions observed in the electronic ground and excited states were simulated by calculating Franck-Condon factors based on the neutral as well as the cation ground and excited state geometries. iPEPICO was used to obtain ion dissociation data in threshold photoionization as a function of photon energy, which were modeled with RRKM theory to extract kinetic parameters for the reactions C9H8(+•) (1-propynylbezene) → C9H7(+) + H (R1); C9H8(+•) (indene) → C9H7(+) + H (R2); C8H8(+•) (benzocyclobutene) → C8H7(+) + H (R3); C8H8(+•) (benzocyclobutene) → C6H6(+) + C2H2 (R4); C8H6(+•) (1-ethynylbenzene, aka phenylacetylene) → C6H4(+) + C2H2 (R5). These results were compared to G3 level calculations. In addition, the enthalpy of formation of the indenyl radical was estimated to be ΔfH°0K = 249 ± 50 kJ mol(-1) based on a previously measured IE and a cation ΔfH°0K = 976 kJ mol(-1), determined herein.

Photoionization of cold gas phase coronene and its clusters: autoionization resonances in monomer, dimer, and trimer and electronic structure of monomer cation.

Polycyclic aromatic hydrocarbons (PAHs) are key species encountered in a large variety of environments such as the Interstellar Medium (ISM) and in combustion media. Their UV spectroscopy and photodynamics in neutral and cationic forms are important to investigate in order to learn about their structure, formation mechanisms, and reactivity. Here, we report an experimental photoelectron-photoion coincidence study of a prototypical PAH molecule, coronene, and its small clusters, in a molecular beam using the vacuum ultraviolet (VUV) photons provided by the SOLEIL synchrotron facility. Mass-selected high resolution threshold photoelectron (TPES) and total ion yield spectra were obtained and analyzed in detail. Intense series of autoionizing resonances have been characterized as originating from the monomer, dimer, and trimer neutral species, which may be used as spectral fingerprints for their detection in the ISM by VUV absorption spectroscopy. Finally, a full description of the electronic structure of the monomer cation was made and discussed in detail in relation to previous spectroscopic optical absorption data. Tentative vibrational assignments in the near-threshold TPES spectrum of the monomer have been made with the support of a theoretical approach based on density functional theory.

The threshold photoelectron spectroscopy of the cis- and trans- 1-chloro 2-fluoro-ethene isomers: an experimental and quantum chemical study

The threshold photoelectron spectra (TPES) of the two vicinal isomers of the 1,2-C2H2FCl molecule have been investigated in the 9–24 eV energy range using synchrotron radiation. Eight (for the cis-isomer) or nine (for the trans-isomer) bands have been observed and the corresponding ionization energies have been determined. The spectroscopic assignments are based on high level quantum chemical ab initio calculations for both isomers. Most of the observed spectral features could be interpreted. For both species the first three TPES bands exhibit a rich vibrational structure. Vibrational energies were determined and assignments were also supported by quantum chemical calculations of vibrational wavenumbers for these three ionic states of both isomers.

High-resolution threshold photoelectron and photoion spectroscopy of molecular nitrogen in the 15.0–52.7 eV photon energy range

We have performed an extensive study of the threshold photoelectron spectrum of N2 over the valence ionization region 15.0–28.0eV under high-resolution conditions. In addition, we measured the high-resolution photoion spectrum of N2 over the same photon energy range. These complimentary views of ionization in molecular systems provide different perspectives of the mechanism for the production of both ions and threshold electrons. The studies are presented in the context of our current understanding of the relationship between: (i) the autoionization of neutral Rydberg states and direct photoionization to (ii) the production of electrons and the ionic states of nitrogen at threshold. In both cases (ions and threshold electrons) we have found a considerable amount of new information on the vibrational states of a number of neutral and ionic electronic states. The inner valence ionization region of nitrogen was also investigated using threshold photoelectron spectroscopy over the photon energy range (27.7–52.7eV) and is presented from the perspective of the formation of mixed-configuration ionic satellite states and the possibility of the involvement of ionic Rydberg states converging on the double ionization of nitrogen.