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From photoelectron detachment spectra of BrHBr{sup −}, BrDBr{sup −} and IHI{sup −}, IDI{sup −} to vibrational bonding of BrMuBr and IMuI
Photoelectron detachment XLX{sup −}(00{sup 0}0) + hν → XLX(vib) + e{sup −} + KER (X = Br or I, L = H or D) at sufficiently low temperatures photoionizes linear dihalogen anions XLX{sup −} in the vibrational ground state (v{sub 1}v{sub 2}{sup l}v{sub 3} = 00{sup 0}0) and prepares the neutral radicals XLX(vib) in vibrational states (vib). At the same time, part of the photon energy (hν) is converted into kinetic energy release (KER) of the electron [R. B. Metz, S. E. Bradforth, and D. M. Neumark, Adv. Chem. Phys. 81, 1 (1992)]. The process may be described approximately in terms of a Franck-Condon type transfer of the vibrational wavefunction representing XLX{sup −}(00{sup 0}0) from the domain close to the minimum of its potential energy surface (PES) to the domain close to the linear transition state of the PES of the neutral XLX. As a consequence, prominent peaks of the photoelectron detachment spectra (pds) correlate with the vibrational energies E{sub XLX,vib} of states XLX(vib) which are centered at linear transition state. The corresponding vibrational quantum numbers may be labeled vib = (v{sub 1}v{sub 2}{sup l}v{sub 3}) = (00{sup 0}v{sub 3}). Accordingly, the related most prominent peaks in the pds are labeled v{sub 3}. We construct a model PES which mimics the “true” PES in the domain of transition state such that it supports vibrational states with energies E{sub XLX,pds,00{sup 0}v{sub 3}} close to the peaks of the pds labeled v{sub 3} = 0, 2, and 4. Subsequently, the same model PES is also used to calculate approximate values of the energies E{sub XMuX,00{sup 0}0} of the isotopomers XMuX(00{sup 0}0). For the heavy isotopomers XHX and XDX, it turns out that all energies E{sub XLX,00{sup 0}v{sub 3}} are above the threshold for dissociation, which means that all heavy XLX(00{sup 0}v{sub 3}) with wavefunctions centered at the transition state are unstable resonances with finite lifetimes. Turning the table, bound states of the heavy XLX are van der Waals (vdW) bonded. In contrast, the energies E{sub XMuX,00{sup 0}0} of the light isotopomers XMuX(00{sup 0}0) are below the threshold for dissociation, with wavefunctions centered at the transition state. This means that XMuX(00{sup 0}0) are vibrationally bonded. This implies a fundamental change of the nature of chemical bonding, from vdW bonding of the heavy XHX, XDX to vibrational bonding of XMuX. For BrMuBr, the present results derived from experimental pds of BrHBr{sup −} and BrDBr{sup −} confirm the recent discovery of vibrational bonding based on quantum chemical ab initio calculations [D. G. Fleming, J. Manz, K. Sato, and T. Takayanagi, Angew. Chem., Int. Ed. 53, 13706 (2014)]. The extension from BrLBr to ILI means the discovery of a new example of vibrational bonding. These empirical results for the vibrational bonding of IMuI, derived from the photoelectron spectra of IHI{sup −} and IDI{sup −}, are supported by ab initio simulations of the spectra and of the wavefunction representing vibrational bonding of IMuI.
Electronic damage in S atoms in a native protein crystal induced by an intense X-ray free-electron laser pulse
Current hard X-ray free-electron laser (XFEL) sources can deliver doses to biological macromolecules well exceeding 1 GGy, in timescales of a few tens of femtoseconds. During the pulse, photoionization can reach the point of saturation in which certain atomic species in the sample lose most of their electrons. This electronic radiation damage causes the atomic scattering factors to change, affecting, in particular, the heavy atoms, due to their higher photoabsorption cross sections. Here, it is shown that experimental serial femtosecond crystallography data collected with an extremely bright XFEL source exhibit a reduction of the effective scattering power of the sulfur atoms in a native protein. Quantitative methods are developed to retrieve information on the effective ionization of the damaged atomic species from experimental data, and the implications of utilizing new phasing methods which can take advantage of this localized radiation damage are discussed.
Fragmentation of mercury compounds under ultraviolet light irradiation
Ultraviolet light induced photofragmentation of mercury compounds is studied experimentally with electron energy resolved photoelectron-photoion coincidence techniques and theoretically with computational quantum chemical methods. A high resolution photoelectron spectrum using synchrotron radiation is presented. Fragmentation of the molecule is studied subsequent to ionization to the atomic-mercury-like d orbitals. State dependent fragmentation behaviour is presented and specific reactions for dissociation pathways are given. The fragmentation is found to differ distinctly in similar orbitals of different mercury compounds.
A complete map of the ion chemistry of the naphthalene radical cation? DFT and RRKM modeling of a complex potential energy surface
The fragmentation mechanisms of the naphthalene molecular ion to [M–C{sub 4}H{sub 2}]{sup +•}, [M–C{sub 2}H{sub 2}]{sup +•}, [M–H{sub 2}]{sup +•}, and [M–H{sup •}]{sup +} were obtained at the UB3LYP/6-311+G(3df,2p)//UB3LYP/6-31G(d) level of theory and were subsequently used to calculate the microcanonical rate constants, k(E)’s, for all the steps by the Rice-Ramsperger-Kassel-Marcus formalism. The pre-equilibrium and steady state approximations were applied on different regions of the potential energy profiles to obtain the fragmentation k(E)’s and calculate the relative abundances of the ions as a function of energy. These results reproduce acceptably well the imaging photoelectron-photoion coincidence spectra of naphthalene, in the photon-energy range 14.0–18.8 eV that was previously reported by our group. Prior to dissociation, the molecular ion rapidly equilibrates with a set of isomers that includes the Z- and E-phenylvinylacetylene (PVA) radical cations. The naphthalene ion is the predominant isomer below 10 eV internal energy, with the other isomers remaining at steady state concentrations. Later on, new steady-state intermediates are formed, such as the azulene and 1-phenyl-butatriene radical cations. The naphthalene ion does not eject an H atom directly but eliminates an H{sub 2} molecule in a two-step fragmentation. H{sup •} loss occurs instead from the 1-phenyl-butatriene ion. The PVA ions initiate the ejection of diacetylene (C{sub 4}H{sub 2}) to yield the benzene radical cation. Acetylene elimination yields the pentalene cation at low energies (where it can account for 45.9%–100.0% of the rate constant of this channel), in a three-step mechanism starting from the azulene ion. However, above 7.6 eV, the major [M–C{sub 2}H{sub 2}]{sup +•} structure is the phenylacetylene cation.
Nanocluster ionization energies and work function of aluminum, and their temperature dependence
Ionization threshold energies of Al{sub n} (n = 32-95) nanoclusters are determined by laser ionization of free neutral metal clusters thermalized to several temperatures in the range from 65 K to 230 K. The photoion yield curves of cold clusters follow a quadratic energy dependence above threshold, in agreement with the Fowler law of surface photoemission. Accurate data collection and analysis procedures make it possible to resolve very small (few parts in a thousand) temperature-induced shifts in the ionization energies. Extrapolation of the data to the bulk limit enables a determination of the thermal shift of the polycrystalline metal work function, found to be in excellent agreement with theoretical prediction based on the influence of thermal expansion. Small clusters display somewhat larger thermal shifts, reflecting their greater susceptibility to thermal expansion. Ionization studies of free size-resolved nanoclusters facilitate understanding of the interplay of surface, electronic, and lattice properties under contamination-free conditions.
A joint theoretical and experimental study on diiodomethane: Ions and neutrals in the gas phase
The chemical physics of halomethanes is an important and challenging topic in several areas of chemistry in particular in the chemistry of the atmosphere. Among the class of halomethanes, the diiodomethane molecule has attracted some interest in the last years, but despite this, the information on its radical cation [CH{sub 2}I{sub 2}]{sup ⋅+} is still limited. In this work, we measured and calculated the appearance energy (AE) of the ionic fragments I{sub 2}{sup ⋅+} and CH{sub 2}{sup ⋅+} and correlated the different fragmentation channels to the electronic states of the cation via photoelectron-photoion coincidence (PEPICO) experiments. In the case of the CH{sub 2}/I{sub 2}{sup ⋅+} channel, the experimentally determined AE is in excellent agreement with the adiabatic theoretical value while a discrepancy is observed for the CH{sub 2}{sup ⋅+}/I{sub 2} channel. This discrepancy can be understood accounting for a fragmentation involving the formation of two I atoms (CH{sub 2}{sup ⋅+}/2I channel), which, as explained by time dependent density functional theory (TD-DFT) calculations, occurs when [CH{sub 2}I{sub 2}]{sup ⋅+} excited states are involved.
On the ultrafast photo-induced dynamics of α-terpinene
The ultrafast relaxation pathway of α-terpinene was studied by photoionization-photoelectron spectroscopy for a range of excitation conditions. Time-resolved spectra were obtained upon optical excitation with ultrashort laser pulses at 5.56 eV, 4.96 eV, 4.76 eV, and 4.56 eV, followed by ionization with 3.06 eV pulses. The experiments yielded spectra of the initially excited state, which decays with a time constant of 66 fs, independent of the excitation wavelength. We also observed a sequential series of Rydberg peaks, including the s, p, and d states with n = 3–6, which capture the travel times on the ensuing reaction path. There is no statistically significant dependence of the travel time on the excitation energy. A comparison of the time-dependent signals with those of the un-substituted parent molecule, 1,3-cyclohexadiene, shows that the substituents on α-terpinene slow the reaction down by a factor of about 2.
Increasing the applicability of density functional theory. V. X-ray absorption spectra with ionization potential corrected exchange and correlation potentials
Core excitation energies are computed with time-dependent density functional theory (TD-DFT) using the ionization energy corrected exchange and correlation potential QTP(0,0). QTP(0,0) provides C, N, and O K-edge spectra to about an electron volt. A mean absolute error (MAE) of 0.77 and a maximum error of 2.6 eV is observed for QTP(0,0) for many small molecules. TD-DFT based on QTP (0,0) is then used to describe the core-excitation spectra of the 22 amino acids. TD-DFT with conventional functionals greatly underestimates core excitation energies, largely due to the significant error in the Kohn-Sham occupied eigenvalues. To the contrary, the ionization energy corrected potential, QTP(0,0), provides excellent approximations (MAE of 0.53 eV) for core ionization energies as eigenvalues of the Kohn-Sham equations. As a consequence, core excitation energies are accurately described with QTP(0,0), as are the core ionization energies important in X-ray photoionization spectra or electron spectroscopy for chemical analysis.
Dissociation of multiply charged ICN by Coulomb explosion
The fragmentations of iodine cyanide ions created with 2 to 8 positive charges by photoionization from inner shells with binding energies from 59 eV (I 4d) to ca. 900 eV (I 3p) have been examined by multi-electron and multi-ion coincidence spectroscopy with velocity map imaging ion capability. The charge distributions produced by hole formation in each shell are characterised and systematic effects of the number of charges and of initial charge localisation are found.
Breaking through the false coincidence barrier in electron–ion coincidence experiments
Photoelectron Photoion Coincidence (PEPICO) spectroscopy holds the promise of a universal, isomer-selective, and sensitive analytical technique for time-resolved quantitative analysis of bimolecular chemical reactions. Unfortunately, its low dynamic range of ~10 3 has largely precluded its use for this purpose, where a dynamic range of at least 10 5 is generally required. This limitation is due to the false coincidence background common to all coincidence experiments, especially at high count rates. Electron/ion pairs emanating from separate ionization events but arriving within the ion time of flight (TOF) range of interest constitute the false coincidence background. Although this background has uniform intensity at every m/z value, the Poisson scatter in the false coincidence background obscures small signals. In this paper, temporal ion deflection coupled with a position-sensitive ion detector enables suppression of the false coincidence background, increasing the dynamic range in the PEPICO TOF mass spectrum by 2–3 orders of magnitude. The ions experience a time-dependent electric deflection field at a well-defined fraction of their time of flight. This deflection defines an m/z- and ionization-time dependent ion impact position for true coincidences, whereas false coincidences appear randomly outside this region and can be efficiently suppressed. When cold argon clusters are ionized, false coincidence suppression allows us to observe species up to Ar 9 + , whereas Ar 4 + is the largest observable cluster under traditional operation. As a result, this advance provides mass-selected photoelectron spectra for fast, high sensitivity quantitative analysis of reacting systems.
A small porous-plug burner for studies of combustion chemistry and soot formation
We have developed and built a small porous-plug burner based on the original McKenna burner design. The new burner generates a laminar premixed flat flame for use in studies of combustion chemistry and soot formation. The size is particularly relevant for space-constrained, synchrotron-based X-ray diagnostics. In this paper, we present details of the design, construction, operation, and supporting infrastructure for this burner, including engineering attributes that enable its small size. We also present data for charactering the flames produced by this burner. These data include temperature profiles for three premixed sooting ethylene/air flames (equivalence ratios of 1.5, 1.8, and 2.1); temperatures were recorded using direct one-dimensional coherent Raman imaging. We include calculated temperature profiles, and, for one of these ethylene/air flames, we show the carbon and hydrogen content of heavy hydrocarbon species measured using an aerosol mass spectrometer coupled with vacuum ultraviolet photoionization (VUV-AMS), and soot-volume-fraction measurements obtained using laserinduced incandescence (LII). In addition, we provide calculated mole-fraction profiles of selected gas-phase species and characteristic profiles for seven mass peaks from AMS measurements. Using these experimental and calculated results, we discuss the differences between standard McKenna burners and the new miniature porous-plug burner introduced here.
Auger electron angular distributions following excitation or ionization of the I 3d level in methyl iodide
Auger electron spectra following excitation or ionization of the I 3d level in CH 3 I have been recorded with horizontally or vertically plane polarized synchrotron radiation. These spectra have enabled the Auger electron angular distributions, as characterized by the β parameter, to be determined. The I 3d photoionization partial cross section of CH 3 I has been calculated with the continuum multiple scattering approach, and the results show that in the photon energy range over which Auger spectra were measured, the I 3d cross section exhibits an atomic-like behavior and is dominated by transitions into the εf continuum channel. In this limit, the theoretical value of the alignment parameter (A 20 ) characterizing the core ionized state in an atom becomes constant, independent of photon energy. This theoretical value has been used to obtain the Auger electron intrinsic anisotropy parameters (α 2 ) from the β parameters extracted from our normal (non-resonant) molecular Auger spectra. The resulting anisotropy parameters for the M 45 N 45 N 45 transitions in CH 3 I have been compared to those calculated for the corresponding transitions in xenon, and the experimental and theoretical results are in good agreement. Anisotropy parameters have also been measured for the M 45 N 1 N 45 , M 45 N 23 N 45 , and M 45 N 45 O 23 transitions. For the M 45 N 1 N 45 and M 45 N 23 N 45 Auger decays in CH 3 I, the experimentally derived angular distributions do not exhibit the strong dependence on the final ionic state that is predicted for these transitions in xenon. Resonantly excited Auger spectra have been recorded at 620.4 and 632.0 eV, coinciding with the I 3d 5/2 → σ* and 3d 3/2 → σ* transitions, respectively. The resulting Auger electron angular distributions for the M 4 N 45 N 45 and M 5 N 45 N 45 decays were found to exhibit a higher anisotropy than those for the normal process. This is due to the larger photo-induced alignment in the neutral core excited state. For a particular Auger transition, the Auger electron kinetic energy measured in the resonantly excited spectrum is higher than that in the normal spectrum. This shift, due to the screening provided by the electron excited into the σ* orbital, has been rationalized by calculating orbital ionization energies of I 3d excited and I 3d ionized states in CH 3 I.
Fundamental understanding of chemical processes in extreme ultraviolet resist materials
New photoresists are needed to advance extreme ultraviolet (EUV) lithography. The tailored design of efficient photoresists is enabled by a fundamental understanding of EUV induced chemistry. Processes that occur in the resist film after absorption of an EUV photon are discussed, and a new approach to study these processes on a fundamental level is described. The processes of photoabsorption, electron emission, and molecular fragmentation were studied experimentally in the gas-phase on analogs of the monomer units employed in chemically amplified EUV resists. To demonstrate the dependence of the EUV absorption cross section on selective light harvesting substituents, halogenated methylphenols were characterized employing the following techniques. Photoelectron spectroscopy was utilized to investigate kinetic energies and yield of electrons emitted by a molecule. The emission of Auger electrons was detected following photoionization in the case of iodo-methylphenol. Mass-spectrometry was used to deduce the molecular fragmentation pathways following electron emission and atomic relaxation. To gain insight on the interaction of emitted electrons with neutral molecules in a condensed film, the fragmentation pattern of neutral gas-phase molecules, interacting with an electron beam, was studied and observed to be similar to EUV photon fragmentation. Below the ionization threshold, electrons were confirmed to dissociate iodo-methylphenol by resonant electron attachment.
Pulse analysis by delayed absorption from a coherently excited atom
In this tutorial, we provide a short review of attosecond pulse characterization techniques and a pedagogical account of a recently proposed method called Pulse Analysis by Delayed Absorption (PANDA) [S. Pabst and J. M. Dahlstr¨om, Phys. Rev. A 94, 013411 (2016)]. We discuss possible implementations of PANDA in alkali atoms using either principal quantum number wave packets or spin-orbit wave packets. The main merit of the PANDA method is that it can be used as a pulse characterization method that is free from atomic latency effects, such as scattering phase shifts and long-lived atomic resonances. Finally, we propose that combining the PANDA method with angle-resolved photoelectron detection should allow for experimental measurements of attosecond delays in photoionization from bound wave packets on the order of tens of attoseconds.
Simulated XUV photoelectron spectra of THz-pumped liquid water
Highly intense, sub-picosecond terahertz (THz) pulses can be used to induce ultrafast temperature jumps (T-jumps) in liquid water. A supercritical state of gas-like water with liquid density is established, and the accompanying structural changes are expected to give rise to time-dependent chemical shifts. We investigate the possibility of using extreme ultraviolet photoelectron spectroscopy as a probe for ultrafast dynamics induced by sub-picosecond THz pulses of varying intensities and frequencies. To this end, we use ab initio methods to calculate photoionization cross sections and photoelectron energies of (H 2 O) 20 clusters embedded in an aqueous environment represented by point charges. The cluster geometries are sampled from ab initio molecular dynamics simulations modeling the THz-water interactions. Here we find that the peaks in the valence photoelectron spectrum are shifted by up to 0.4 eV after the pump pulse and that they are broadened with respect to unheated water. The shifts can be connected to structural changes caused by the heating, but due to saturation effects they are not sensitive enough to serve as a thermometer for T-jumped water.
Ultrafast photodissociation dynamics and nonadiabatic coupling between excited electronic states of methanol probed by time-resolved photoelectron spectroscopy
The electronic and nuclear dynamics in methanol, following 156 nm photoexcitation, are investigated by combining a detailed analysis of time-resolved photoelectron spectroscopy experiments with electronic structure calculations. The photoexcitation pump pulse is followed by a delayed 260 nm photoionization probe pulse to produce photoelectrons that are analyzed by velocity map imaging. The yields of mass-resolved ions, measured with similar experimental conditions, are found to exhibit the same time-dependence as specific photoelectron spectral features. Energy-resolved signal onset and decay times are extracted from the measured photoelectron spectra to achieve high temporal resolution, beyond the 20 fs pump and probe pulse durations. When combined with ab initio calculations of selected cuts through the excited state potential energy surfaces, this information allows the dynamics of the transient excited molecule, which exhibits multiple nuclear and electronic degrees of freedom, to be tracked on its intrinsic few-femtosecond time scale. Within 15 fs of photoexcitation, we observe nuclear motion on the initially bound photoexcited 2 1 A" (S 2 ) electronic state, through a conical intersection with the 1 1 A' (S3) state, which reveals paths to photodissociation following C–O stretch and C–O–H angle opening.
Excited state dynamics of CH 2 I 2 and CH 2 BrI studied with UV pump VUV probe photoelectron spectroscopy
We compare the excited state dynamics of diiodomethane (CH 2 I 2 ) and bromoiodomethane (CH 2 BrI) using time resolved photoelectron spectroscopy. A 4.65 eV UV pump pulse launches a dissociative wave packet on excited states of both molecules and the ensuing dynamics are probed via photoionization using a 7.75 eV probe pulse. The resulting photoelectrons are measured with the velocity map imaging technique for each pump-probe delay. Our measurements highlight differences in the dynamics for the two molecules, which are interpreted with high-level ab initio molecular dynamics (trajectory surface hopping) calculations. Our analysis allows us to associate features in the photoelectron spectrum with different portions of the excited state wave packet represented by different trajectories. The excited state dynamics in bromoiodomethane are simple and can be described in terms of direct dissociation along the C–I coordinate, whereas the dynamics in diiodomethane involve internal conversion and motion along multiple dimensions.