Valence Photoionization Research Articles

Electron and ion spectroscopy of azobenzene in the valence and core shells.

Azobenzene is a prototype and a building block of a class of molecules of extreme technological interest as molecular photo-switches. We present a joint experimental and theoretical study of its response to irradiation with light across the UV to x-ray spectrum. The study of valence and inner shell photo-ionization and excitation processes combined with measurement of valence photoelectron-photoion coincidence and mass spectra across the core thresholds provides a detailed insight into the site- and state-selected photo-induced processes. Photo-ionization and excitation measurements are interpreted via the multi-configurational restricted active space self-consistent field method corrected by second order perturbation theory. Using static modeling, we demonstrate that the carbon and nitrogen K edges of azobenzene are suitable candidates for exploring its photoinduced dynamics thanks to the transient signals appearing in background-free regions of the NEXAFS and XPS.

Electronic state influence on selective bond breaking of core-excited nitrosyl chloride (ClNO).

The potential for selective bond breaking of a small molecule was investigated with electron spectroscopy and electron-ion coincidence experiments on ClNO. The electron spectra were measured upon direct valence photoionization and resonant core excitation at the N 1s- and O 1s-edges, followed by the emission of resonant-Auger (RA) electrons. The RA spectra were analyzed with particular emphasis on the assignment of the participator and spectator states. The states are of special relevance for investigating how distinct electronic configurations influence selective bond breaking. The electron-ion coincidence measurements provided branching fractions of the produced ion fragments as a function of electron binding energy. They explicitly demonstrate how the final electronic states created after photoionization and RA decay influence fragmentation. In particular, we observed a significantly different branching fraction for spectator states compared with participator states. In addition, it was also observed that the bonds broken for the spectator states correlate with the antibonding nature of the spectator-electron orbital.

Inner-shell photoabsorption and photoionisation cross-sections of valence excited states from asymmetric-Lanczos equation-of-motion coupled cluster singles and doubles theory

The asymmetric-Lanczos-based equation-of-motion coupled cluster formalism to compute photoabsorption and photoionisation cross-sections of valence excited states [B.N.C. Tenorio, M.A.C. Nascimento, A.B. Rocha, and S. Coriani, J. Chem. Phys. 151 (18), 184106 (2019). doi:10.1063/1.5125125] has been adapted to enable the calculation of photoabsorption and photoionisation spectral signatures from inner-shell electrons of such states. Since excited-state properties depend on both the electronic character of the molecular wavefunction and on the nuclear dynamics, we computed the photoionisation spectra using both ground and excited state optimised geometries. The total cross-section profiles were generated for the first two electronically excited states of water, ammonia, ethylene, and uracil by two different methodologies: an analytic continuation procedure based on the Padé approximants and by the Stieltjes imaging procedure. A comparison with literature results, whenever available, is presented. Remarkable differences were observed between the results of the core-ionisation cross-sections of the valence excited states yielded by the two quadrature approaches, at variance from previous studies on the valence photoionisation cross-sections of ground states and of valence excited states. Their origin remains unclear.

Valence Photoionization and Energetics of Vanillin, a Sustainable Feedstock Candidate.

We studied the valence photoionization of vanillin by photoelectron photoion coincidence spectroscopy in the 8.20-19.80 eV photon energy range. Vertical ionization energies by EOM-IP-CCSD calculations reproduce the photoelectron spectral features. Composite method calculations and Franck-Condon simulation of the weak, ground-state band yield the adiabatic ionization energy of the most stable vanillin conformer as 8.306(20) eV. The lowest energy dissociative photoionization channels correspond to hydrogen atom, carbon monoxide, and methyl losses, which form the dominant C8H7O3+ (m/z 151) and the less intense C7H8O2+ (m/z 124) and C7H5O3+ (m/z 137) fragment ions in parallel dissociation channels at modeled 0 K appearance energies of 10.13(1), 10.40(3), and 10.58(10) eV, respectively. On the basis of the breakdown diagram, we explore the energetics of sequential methyl and carbon monoxide loss channels, which dominate the fragmentation mechanism at higher photon energies. The 0 K appearance energy for sequential CO loss from the m/z 151 fragment to C7H7O2+ (m/z 123) is 12.99(10) eV, and for sequential CH3 loss from the m/z 123 fragment to C6H4O2+ (m/z 108), it is 15.40(20) eV based on the model. Finally, we review the thermochemistry of the bi- and trifunctionalized benzene derivatives guaiacol, hydroxybenzaldehyde, anisaldehyde, and vanillin. On the basis of isodesmic functional group exchange reactions, we propose new enthalpies of formations, among them ΔfH°298K(vanillin, g) = -383.5 ± 2.9 kJ mol-1. These mechanistic insights and ab initio thermochemistry results will support analytical works to study lignin conversion involving vanillin.

From Energetics to Intracluster Chemistry: Valence Photoionization of Trifluoromethylsulfur Pentafluoride (CF3SF5) by Double Velocity Map Imaging.

Trifluoromethylsulfur pentafluoride (CF3SF5) was valence threshold photoionized in a double imaging photoelectron photoion coincidence spectrometer using vacuum ultraviolet synchrotron radiation. In the 12.5-16.4 eV photon energy range, CF3+, SF5+, and SF3+ cations were observed in both room temperature (RT) and molecular beam (MB) experiments. Their fractional abundances exhibited differences beyond the sample temperature. Kinetic energy analysis of the fragment ions confirmed the difference in the dissociative photoionization mechanism. In the RT experiment, the CF3+ kinetic energies were extrapolated to a 11.84 ± 0.15 eV threshold, which was used in an ion cycle to determine the enthalpy of formation of CF3SF5 as ΔfH°298K(CF3SF5) = -1593 ± 16 kJ mol-1. We also updated the enthalpy of formation of the sulfur pentafluoride radical as ΔfH°298K(SF5) = -854 ± 7 kJ mol-1 and discuss the discrepancy between the CF3 ionization energy based on the Active Thermochemical Tables and the value anchored to the CF ionization energy. A computed reaction enthalpy network optimization resulted in ΔfH°298K(CF3SF5) = -1608 ± 20 kJ mol-1. Both values for ΔfH°298K(CF3SF5) agree with previous ab initio ones in contrast to the original, experimental determination. SF3+ is formed by F-transfer processes both in the RT and MB experiments. Although the same peaks were observed in both experiments, the lower SF3+ onset energy and the more slowly rising CF3+ kinetic energy release in the MB experiment revealed clustering and intracluster F-transfer reactions upon ionization. The monomer and dimer cation potential energy surfaces were explored to rationalize the observations. In the dimer cation, the observer CF3SF5 catalyzes fluorine transfer and promotes CF4 formation, which ultimately leads to the SF3+ fragment ion.

Electron–ion coincidence spectroscopy of a large organic molecule: photofragmentation of avobenzone after valence and core ionisation

The Avobenzone (AVOB) molecule is very photoactive and undergoes irreversible degradation upon irradiation. We studied its valence and core-level (C1s and O1s) photoionisation and subsequent photofragmentation with photoelectron spectroscopy and photoelectron–photoion–photoion coincidence (PEPIPICO) spectroscopy. AVOB is one of the largest molecules studied with this technique. The results show that the AVOB molecule dissociates into an extensive range of fragments by different pathways with little element or site-selectivity. The coincident maps were used to determine selected fragment separation sequences by analysing the slopes of patterns from ion pairs after the core ionisation. Charge delocalisation over the benzene rings and their relative stability favor fragmentation by cleavage of the bridge between them.

A study of the valence shell absolute photoabsorption, photoionization and photodissociation cross sections, and the photoionization quantum efficiency of carbon monoxide

The spectroscopic characteristics and the decay mechanisms of the Rydberg states arising from valence shell excitations in carbon monoxide have been investigated by using a double ion chamber and synchrotron radiation to measure the absolute photoabsorption, photoionization and photodissociation cross sections, and the photoionization quantum efficiency, in the energy range between the ionization threshold and 36 eV. Guided by earlier theoretical predictions, the prominent absorption bands due to Rydberg states belonging to series converging onto the A 2Π state ionization threshold have been assigned, in accord with previous studies, to the ndδ and the [(n + 1)s + nd]σ transitions. Apart from the (4s + 3d)σ state which decays predominantly by predissociation into neutral fragments, most of the Rydberg states belonging to these series decay preferentially by autoionization. Another Rydberg series converging onto the A 2Π state limit has been tentatively assigned to the npσ transitions, even though these transitions are predicted to be weak. The v′ = 0 and v′ = 1 vibrational levels of the 4pσ state decay preferentially by predissociation into neutral fragments. The [(n + 1)s − nd]σ transitions are also calculated to be weak but may be associated with some previously unassigned absorption bands. Structure observed in the absorption spectrum between ∼19.5 and 23.5 eV may be due to Rydberg states associated with series converging onto the D 2Π or the 3 2Σ+ state limits. This structure is discussed in relation to dispersed fluorescence spectra and negative ion yields recorded over the same energy range.

Vibrationally resolved valence and core photoionization and photoexcitation spectra of an electron-deficient trivalent boron compound: the case of catecholborane.

Compounds containing trivalent boron (TB) as the electron-deficient site(s) find numerous practical uses ranging from Lewis bases in organic synthesis to high-tech industry, with a number of novel applications anticipated. We present an experimental and theoretical study of the gas-phase valence photoionization (VUV-PES), core photoionization (XPS) and photoexcitation (NEXAFS) spectra of a representative TB compound catecholborane (CB). For modelling and assigning the spectra we used the ΔDFT and restricted single excitation space TD-DFT methods for the XPS and NEXAFS, and OVGF and EOM-CCSD for the VUV-PES. The vibrationally resolved structure was computed in the Franck-Condon (FC) and Herzberg-Teller (FCHT) approximations generally resulting in a good agreement with the observed spectral features. For the prediction of core-electron binding energies (CEBEs) several density functionals were tested. The best performance overall was furnished by ωB97X-D suggesting that including the dispersion correction is beneficial. The FCHT vibronic intensities are in clear discrepancy with the B 1s NEXAFS spectrum if the harmonic approximation is used for the B-H wagging mode both in the ground and in the first core-excited state. Instead, a much better agreement is obtained if the excited state potential is approximated to a symmetric double-well. The observed vibronic pattern could be a general fingerprint of the presence of TB centre(s), specifically, the transfer of the (core) density to the vacant boron p-orbital in the excited state.

Electronic Decay of Singly Charged Ground-State Ions by Charge Transfer via van der Waals Bonds.

We report the observation of the radiative decay of singly charged noble gas ground-state ions embedded in heterogeneous van der Waals clusters. Electron-photon coincidence spectroscopy and dispersed photon spectroscopy are applied to identify the radiative charge transfer from Kr atoms to a Ne_{2}^{+} dimer, which forms after single valence photoionization of Ne atoms at the surface of a NeKr cluster. This mechanism might be a fundamental decay process of ionized systems in an environment.

Valence Photoionization of Thymine: Ionization Energies, Vibrational Structure, and Fragmentation Pathways from the Slow to the Ultrafast.

The photoionization of thymine has been studied by using vacuum ultraviolet radiation and imaging photoelectron photoion coincidence spectroscopy after aerosol flash vaporization and bulk evaporation. The two evaporation techniques have been evaluated by comparison of the photoelectron spectra and breakdown diagrams. The adiabatic ionization energies for the first four electronic states were determined to be 8.922±0.008, 9.851±0.008, 10.30±0.02, and 10.82±0.01 eV. Vibrational features have been assigned for the first three electronic states with the help of Franck-Condon factor calculations based on density functional theory and wave function theory vibrational analysis within the harmonic approximation. The breakdown diagram of thymine, as supported by composite method ab initio calculations, suggests that the main fragment ions are formed in sequential HNCO-, CO-, and H-loss dissociation steps from the thymine parent ion, with the first step corresponding to a retro-Diels-Alder reaction. The dissociation rate constants were extracted from the photoion time-of-flight distributions and used together with the breakdown curves to construct a statistical model to determine 0 K appearance energies of 11.15±0.16 and 11.95±0.09 eV for the m/z 83 and 55 fragment ions, respectively. These results have allowed us to revise previously proposed fragmentation mechanisms and to propose a model for the final, nonstatistical H-loss step in the breakdown diagram, yielding the m/z 54 fragment ion at an appearance energy of 13.24 eV.

Attosecond time delays in the valence photoionization of xenon and iodine at energies degenerate with core emissions

SynopsisWe perform time-dependent local density functional calculations of the quantum phase and Wigner-Smith time delays in the valence photoionization of Xe versus I atoms at higher energies where coupling with the core emission becomes important. Results for the 5s emission are presented.

Assessment of Electron Propagator Methods for the Simulation of Vibrationally Resolved Valence and Core Photoionization Spectra.

The analysis of photoelectron spectra is usually facilitated by quantum mechanical simulations. Because of the recent improvement of experimental techniques, the resolution of experimental spectra is rapidly increasing, and the inclusion of vibrational effects is usually mandatory to obtain a reliable reproduction of the spectra. With the aim of defining a robust computational protocol, a general time-independent formulation to compute different kinds of vibrationally resolved electronic spectra has been generalized to also support photoelectron spectroscopy. The electronic structure data underlying the simulation are computed using different electron propagator approaches. In addition to the more standard approaches, a new and robust implementation of the second-order self-energy approximation of the electron propagator based on a transition operator reference (TOEP2) is presented. To validate our implementation, a series of molecules has been used as test cases. The result of the simulations shows that, for ultraviolet photoionization spectra, the more accurate nondiagonal approaches are needed to obtain a reliable reproduction of vertical ionization energies but that diagonal approaches are sufficient for energy gradients and pole strengths. For X-ray photoelectron spectroscopy, the TOEP2 approach, besides being more efficient, is also the most accurate in the reproduction of both vertical ionization energies and vibrationally resolved bandshapes.

Excited state X-ray absorption spectroscopy: Probing both electronic and structural dynamics.

We investigate the sensitivity of X-ray absorption spectra, simulated using a general method, to properties of molecular excited states. Recently, Averbukh and co-workers [M. Ruberti et al., J. Chem. Phys. 140, 184107 (2014)] introduced an efficient and accurate L2 method for the calculation of excited state valence photoionization cross-sections based on the application of Stieltjes imaging to the Lanczos pseudo-spectrum of the algebraic diagrammatic construction (ADC) representation of the electronic Hamiltonian. In this paper, we report an extension of this method to the calculation of excited state core photoionization cross-sections. We demonstrate that, at the ADC(2)x level of theory, ground state X-ray absorption spectra may be accurately reproduced, validating the method. Significantly, the calculated X-ray absorption spectra of the excited states are found to be sensitive to both geometric distortions (structural dynamics) and the electronic character (electronic dynamics) of the initial state, suggesting that core excitation spectroscopies will be useful probes of excited state non-adiabatic dynamics. We anticipate that the method presented here can be combined with ab initio molecular dynamics calculations to simulate the time-resolved X-ray spectroscopy of excited state molecular wavepacket dynamics.

A study of the valence shell absolute photoabsorption, photoionisation and photodissociation cross sections and the photoionisation quantum efficiency of carbonyl sulphide

The absolute photoabsorption, photoionisation and photodissociation cross sections and the photoionisation quantum efficiency of carbonyl sulphide have been measured using a double ion chamber and synchrotron radiation in the energy range from the ionisation threshold to 24eV. In addition to the absorption bands associated with well established Rydberg series, some previously unassigned features have been tentatively attributed to an f-type Rydberg series converging onto the B̃2Σ+ state ionisation threshold. Structure appearing in the photodissociation spectrum has been correlated with that observed in earlier fluorescence yields for emission, due mainly to the CS photofragment, occurring between 160 and 300nm. The photoionisation quantum efficiency reaches a plateau value close to unity for energies above ∼16eV. The predissociation of Rydberg states into neutral fragments does not appear to affect the photoionisation quantum efficiency of carbonyl sulphide to the extent that is commonly observed in other small molecules. A sum rule analysis has been carried out by combining the present absolute photoabsorption measurements with similar data covering the remaining energy regions.

Valence and L-shell photoionization of Cl-like argon using R-matrix techniques

Photoionization cross sections are obtained using the relativistic Dirac Atomic R-matrix Codes (DARC) for all valence and L-shell energy ranges between 27-270eV. A total of 557 levels arising from the dominant configurations 3s$^2$3p$^4$, 3s3p$^5$, 3p$^6$, 3s$^2$3p$^3$[3d, 4s, 4p], 3p$^5$3d, 3s$^2$3p$^2$3d$^2$, 3s3p$^4$3d, 3s3p$^3$3d$^2$ and 2s$^2$2p$^5$3s$^2$3p$^5$ have been included in the target wavefunction representation of the Ar III ion, including up to 4p in the orbital basis. We also performed a smaller Breit-Pauli (BP) calculation containing the lowest 124 levels. Direct comparisons are made with previous theoretical and experimental work for both valence shell and L-shell photoionization. Excellent agreement was found for transitions involving the $^2$P$^{\rm o}$ initial state to all allowed final states for both calculations across a range of photon energies. A number of resonant states have been identified to help analyze and explain the nature of the spectra at photon energies between 250 and 270eV.

Multi-reference approach to the calculation of photoelectron spectra including spin-orbit coupling.

X-ray photoelectron spectra provide a wealth of information on the electronic structure. The extraction of molecular details requires adequate theoretical methods, which in case of transition metal complexes has to account for effects due to the multi-configurational and spin-mixed nature of the many-electron wave function. Here, the restricted active space self-consistent field method including spin-orbit coupling is used to cope with this challenge and to calculate valence- and core-level photoelectron spectra. The intensities are estimated within the frameworks of the Dyson orbital formalism and the sudden approximation. Thereby, we utilize an efficient computational algorithm that is based on a biorthonormal basis transformation. The approach is applied to the valence photoionization of the gas phase water molecule and to the core ionization spectrum of the [Fe(H2O)6](2+) complex. The results show good agreement with the experimental data obtained in this work, whereas the sudden approximation demonstrates distinct deviations from experiments.

Attosecond time delay in the valence photoionization of C240 versus C60

SynopsisWe investigate effects of electron correlations on the attosecond time delay of the photoionization from HOMO and HOMO-1 electrons in C240. A comparison with earlier C60 results assesses the molecular size effect.

Selectivity in the photofragmentation of halo-pyrimidines

SynopsisThe fragmentation of 2Br-, 2Cl- and 5Br-pyrimidine following direct valence photoionization or inner shell excitation and decay has been studied by electron-ion coincidence experiments. The results show that the fragmentation is strongly selective on the final singly charged ion state and the dominant fragmentation patterns correlate to the nearest appearance potential.

Attosecond time delays in the photoionization of noble gas atoms studied in TDLDA

SynopsisWe perform time-dependent local density functional calculations of the quantum phase and time delays of valence photoionization of noble gas atoms. Results may be accessed by XUV-IR interferometric metrology.

Attosecond time delay in valence photoionization and photorecombination of argon: A time-dependent local-density-approximation study

We determine and analyze the quantum phases and time delays in photoionization and photorecombination of valence 3p and 3s electrons of argon using the Kohn-Sham local density functional approach. The time-dependent local density approximation (TDLDA) is used to account for the electron correlation. Resulting attosecond Wigner-Smith time delays show excellent agreements with two recent independent experiments on argon that measured the relative 3s-3p time delay in photoionization [Physical Review Letters {\bf 106}, 143002 (2011)] and the delay in 3p photorecombination [Physical Review Letters {\bf 112}, 153002 (2014)]