Resonant Photoelectron Spectra Research Articles

Constructing 2D/2D g-C3N4/BiOCl Z-scheme heterojunction for synthesis of imines via photocatalytic coupling of benzylamine

Here, 2D/2D Z-scheme heterojunctions, BiOCl/g-C3N4 (CN-B), are successfully prepared for the photocatalytic coupling of benzylamine (BA) to N-benzylidenebenzylamine (NBA) in air atmosphere under visible light. The high conversion (96.1 %) of BA can be achieved over the optimal catalyst (CN-B-1.6), with a selectivity of NBA (95.2 %). The interface charges are redistributed on CN-B because of the strong interaction between BiOCl and g-C3N4, benefiting to the activation of substrates. The results of In situ diffuse reflectance infrared Fourier-transform spectroscopy (in situ DRIFTS), Electron paramagnetic resonance (EPR) and X-ray photoelectron spectra (XPS) reveal that O2 and BA molecules can be activated via coordinating on the interface of CN-B, thus improving the photocatalytic performance. The migrated pathway of photogenerated carriers follows the mechanism of Z-scheme heterojunction, improving the utilization of electrons-holes. Finally, we put forward a possible mechanism at a molecular scale to explain the photocatalytic pathway. This work emphasizes how to create an effective heterojunction photocatalyst for the photocatalytic organic synthesis.

Valence band spectroscopic study of Co-doped TiO2 nanoparticles using synchrotron based advanced spectroscopic techniques

In this work, we investigate the effects of Co-doping and high-temperature annealing from 400° C to 800 °C on the structural, optical, and electronic characteristics of titanium dioxide (TiO2) nanoparticles (NPs). Sol-gel route was adopted to prepare Ti0.95Co0.05O2 (TCO) NPs. The microstructural characterization using transmission electron microscopy suggests that the grain sizes of TCO NPs enhance with annealing temperatures. The selected area electron diffraction patterns of TCO annealed at 400° C, 600° C, and 800° C show the rings which correspond to anatase, mixed, and rutile phases respectively. Energy dispersive X-ray mapping in scanning transmission electron microscopy mode exhibits the distribution of NPs and their elemental compositions. UV–Visible absorption spectra show a prominent shift to the visible region with slight variation in bandgaps. The electron energy loss spectroscopy confirms the divalent and tetravalent nature of Co and Ti ions respectively. The photo-electron spectroscopic measurements mainly valence band and resonant photoelectron spectroscopies were used to investigate the electronic environment of Co ions in the TiO2 matrix. Valence band spectroscopic results of TiO2 NPs demonstrate the role of O-2p-derived states, but for TCO samples, Co-derived states are also seen. The resonant photo-electron spectra indicate that Co 3d ions are strongly hybridized with Ti3+ defective states.

Identifying the Point of Attachment in the Hypercrosslinking of Benzene for the Synthesis of a Nanoporous Polymer as a Superior Adsorbent for High-Pressure CO2 Capture Application

The point of attachment in the hypercrosslinking of benzene using formaldehyde dimethyl acetal as the crosslinker, anhydrous ferric chloride as the catalyst, and 1,2 dichloroethane as the solvent for the synthesis of poly-benz is reported. A fast microwave-assisted synthesis, within a reaction time of 60 min, resulted in the formation of nanoporous poly-benz having a specific surface area of 1168 m2 g–1. A thorough analysis of poly-benz using 13C cross-polarization magic angle spinning nuclear magnetic resonance and X-ray photoelectron spectra has revealed the hypercrosslinking at the meta position of the benzene ring. The synthesized poly-benz further shows a high CO2 capture capacity of 65.3 wt % at 298 K and 30 bar. Various adsorption isotherm models have been fitted at different temperatures up to 30 bar to represent the equilibrium CO2 adsorption data.

Probing the Strong Nonadiabatic Interactions in the Triazolyl Radical Using Photodetachment Spectroscopy and Resonant Photoelectron Imaging of Cryogenically Cooled Anions.

Although the adiabatic potential energy surfaces defined by the Born-Oppenheimer approximation are the cornerstones for understanding the electronic structure and spectroscopy of molecular systems, nonadiabatic effects due to the coupling of electronic states by nuclear motions are common in complex molecular systems. The nonadiabatic effects were so strong in the 1,2,3-triazolyl radical (C2H2N3) that the photoelectron spectrum of the triazolide anion was rendered unassignable and could only be understood using nonadiabatic calculations, involving the four low-lying electronic states of triazolyl. Using photodetachment spectroscopy and resonant photoelectron imaging of cryogenically cooled anions, we are able to completely unravel the complex vibronic levels of the triazolyl radical. Photodetachment spectroscopy reveals a dipole-bound state for the triazolide anion at 172 cm-1 below the detachment threshold and 32 vibrational Feshbach resonances. Resonant photoelectron imaging is conducted by tuning the detachment laser to each of the Feshbach resonances. Combining the photodetachment spectrum and the resonant photoelectron spectra, we are able to assign all 28 vibronic peaks resolved for the triazolyl radical. Fundamental frequencies for 12 vibrational modes of the ground state of the triazolyl radical are measured experimentally. The current study provides unprecedented experimental vibronic information, which will be valuable to verify theoretical models to treat nonadiabatic effects involving multiple electronic states.

Low-lying Dipole Resonances in FeCN−: A Viable Formation Pathway for FeCN− in Space

A low-lying resonance in FeCN− anion was identified through abrupt changes in the spectral dependence of the photoelectron angular distribution. Non-Franck–Condon transitions from the resonance to the neutral FeCN (4Δ), and the corresponding photoelectron angular distributions revealed that the resonance is a dipole scattering state. Significant thermionic electron emission was observed in the resonant photoelectron spectra, indicating a strong coupling of the resonance with the ground state of this triatomic anion and its competition over autodetachment. This low-lying resonance is identified to be an efficient pathway for the formation of FeCN− anion in the outer envelope of IRC+10216. The results in general reveal formation pathways in space for anions with low-lying resonances and large permanent dipole moment.

Achieving an electron transfer photochromic complex for switchable white-light emission

Tuning white-light emission via free radicals is still a challenge in molecular-based functional materials. Herein, a new photoactive Zn2+ oxalate-based chain containing a polypyridine ligand was designed and synthesized with remarkably bifunctional photochromism and photo-actuated greenish white-light emission after UV, sunlight or Xe lamp light irradiation at room temperature. The photo-actuated coloration process was induced by the photogeneration of stable radicals originated from intermolecular electron transfers from oxalate components to the protonated polypyridine units, as demonstrated by UV–vis, IR, electron spin resonance and X-ray photoelectron spectra and magnetic measurements. Importantly, the on/off greenish white light emission (WLE) could be reversibly switched by generation and elimination of radicals via light irradiation and heat treatment, providing a feasible strategy for designing photoswitchable light emission diodes materials.

Probing the Dipole-Bound State in the 9-Phenanthrolate Anion by Photodetachment Spectroscopy, Resonant Two-Photon Photoelectron Imaging, and Resonant Photoelectron Spectroscopy.

Valence-bound anions with a dipolar core can support dipole-bound states (DBSs) below the electron detachment threshold. The highly diffuse DBS observed is usually of σ symmetry with an s-like orbital. Recently, a π-type DBS was observed experimentally in the 9-anthrolate anion (9AT-) and it was shown to be stabilized due to the large anisotropic polarizability of the 9AT core. To confirm the general existence of π-DBS and its structural dependence, here we report an investigation of the 9-phenanthrolate anion (9PT-), which has a different structure and lower symmetry than 9AT-. Photodetachment spectroscopy revealed a DBS 257 cm-1 below the detachment threshold of 9PT- at 19 627 cm-1 (2.4334 eV). Resonant two-photon photoelectron imaging indeed showed a π symmetry for the DBS. Similar to that observed in 9AT-, the π-DBS in 9PT- is also stabilized by the anisotropic polarizability of the 9PT core and accessed via nonadiabatic population transfer from the initially populated σ-DBS. Photodetachment spectroscopy unveiled nine above-threshold vibrational resonances of the DBS, resulting in nine highly non-Franck-Condon resonant photoelectron spectra by tuning the detachment laser to the vibrational resonances. The combination of photodetachment spectroscopy and resonant photoelectron spectroscopy allowed frequencies for nine vibrational modes of the 9-phenathroxy radical to be measured, including the six lowest frequency bending modes.

Photodetachment spectroscopy and resonant photoelectron imaging of cryogenically cooled 1-pyrenolate

We report an investigation of the 1-pyrenolate anion (PyO-) and the 1-pyrenoxy radical (PyO) using photodetachment spectroscopy and resonant photoelectron imaging of cryogenically cooled anions. The electron affinity of PyO is measured to be 2.4772(4) eV (19 980 ± 3 cm-1) from high-resolution photoelectron spectroscopy. Photodetachment spectroscopy reveals a dipole-bound state (DBS) for PyO- 280 cm-1 below the detachment threshold as well as a broad and intense valence excited state (shape resonance) 1077 cm-1 above the detachment threshold. The shape resonance with an excitation energy of 21 055 cm-1 is due to excitation of an electron from the highest occupied molecular orbital of PyO- to its lowest unoccupied molecular orbital in the continuum. Twenty-nine vibrational levels of the DBS are observed, including 27 above-threshold vibrational levels (vibrational Feshbach resonances). Twenty-seven resonant photoelectron spectra are obtained by tuning the detachment laser to the vibrational Feshbach resonances, resulting in highly non-Franck-Condon photoelectron spectra and rich vibrational information. In total, the frequencies of 21 vibrational modes are obtained for the PyO radical by the combination of the photodetachment and resonant photoelectron spectroscopy, including 13 out-of-plane bending modes.

The influence mechanism of HCO3− on fluoride removal by different types of aluminum salts

In order to study the influence mechanism of HCO3− on the fluoride removal by AlCl3 and Al13, the residual fluoride concentration, residual aluminum concentration and pH value in coagulation effluent were measured at different HCO3− concentrations. Electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS) was used to analyze the aluminum species in the supernatant after coagulation, and the flocs collected were analyzed by nuclear magnetic resonance (NMR) and X-ray photoelectron spectra (XPS). The results show that AlCl3 is used as a coagulant, when the concentration of HCO3− increases from 100 mg/L to 300 mg/L, Al3+ and HCO3− are double hydrolyzed to form Al(OH)3 alum flower after adding AlCl3, and the removal rate of fluoride rapidly increases from 9.55 % to 78.0 %. When the concentration of HCO3− increases from 300 mg/L to 1000 mg/L, the precipitation of Al(OH)3 will gradually dissolve to form Al(OH)4− and the removal rate of fluoride drops from 78.0 % to 56.2 %. When Al13 is used as a coagulant, with the increase of HCO3− from 100 mg/L to 1000 mg/L, its double hydrolysis with Al-F complexes is enhanced, resulting in the formed Al6F2, Al7F2 and Al9F3 gradually dissociate, and the removal rate of fluorine decreases from 78.8 % to 59.4 %.

Photodetachment spectroscopy and resonant photoelectron imaging of the 2-naphthoxide anion via dipole-bound excited states.

We report a photodetachment spectroscopy and high-resolution resonant photoelectron imaging study of cryogenically cooled 2-naphthoxide anions (C10H7O-). The photodetachment spectrum revealed a dipole-bound state (DBS) 202(4) cm-1 below the detachment threshold and 38 resonances corresponding to the vibrational levels of the DBS. By tuning the detachment laser to these above-threshold resonances, we obtained 38 resonantly enhanced photoelectron spectra, which were highly non-Franck-Condon as a result of mode-selective vibrational autodetachment from the DBS. The resonances were assigned by comparing the resonant and non-resonant photoelectron spectra, assisted by the computed vibrational frequencies. Specifically, vibrational features with low Franck-Condon factors or from Franck-Condon-forbidden vibrational modes were significantly enhanced in the resonant photoelectron spectra, resulting in much richer spectroscopic information. The electron affinity of the 2-naphthoxy radical was measured accurately to be 19 387(4) cm-1 or 2.4037(5) eV. In addition, a total of 17 vibrational frequencies were obtained for the 2-naphthoxy radical. In particular, seven Franck-Condon-forbidden out-of-plane bending modes, including the two lowest frequency modes (ν48 at 102 cm-1 and ν47 at 171 cm-1), were observed, demonstrating the advantages of combining photodetachment spectroscopy and resonant photoelectron spectroscopy in obtaining vibrational information for polar radical species via DBS.

Probing the Critical Dipole Moment To Support Excited Dipole-Bound States in Valence-Bound Anions.

We report photodetachment spectroscopy and high-resolution photoelectron imaging of para-halogen substituted phenoxide anions, p-XC6H4O- (X = F, Cl, Br, I). The dipole moments of the p-XC6H4O neutral radicals increase from 2.56 to 3.19 D for X = F to I, providing a series of similar molecules to allow the examination of charge-dipole interactions by minimizing molecule-dependent effects. Excited DBSs ([XC6H4O]*-) are observed for the four anions with binding energies of 8, 11, 24, and 53 cm-1, respectively, for X = F to I, below their respective detachment thresholds. The binding energies exhibit a linear correlation with the dipole moments of the neutral radicals, extrapolating to a critical dipole moment of 2.5 D for zero binding energy. Because of the small binding energy of the excited DBS of [FC6H4O]*-, rotational autodetachment is observed to compete with vibrational autodetachment in the resonant photoelectron spectra, resulting in electrons with near zero kinetic energies.

Tautomer‐Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions

AbstractTautomers of the nucleobases play fundamental roles in spontaneous mutations of DNA. Tautomers of neutral cytosine have been studied in the gas phase, but much less is known about charged species. Here, we report the observation and characterization of three tautomers of deprotonated cytosine anions, [trans‐keto‐amino‐N3H‐H8b] (tKAN3H8b−), [cis‐keto‐amino‐N3H‐H8a] (cKAN3H8a−) and [keto‐amino‐H] (KAN1−), produced by electrospray ionization. Excited dipole‐bound states (DBSs) are uncovered for the three anions by photodetachment spectroscopy. Excitations to selected DBS vibrational levels of cKAN3H8a− and tKAN3H8b− yield tautomer‐specific resonant photoelectron spectra. The current study provides further insight into tautomerism of cytosine and suggests a new method to study the tautomers of nucleobases using electrospray ionization and anion spectroscopy.

Tautomer-Specific Resonant Photoelectron Imaging of Deprotonated Cytosine Anions.

Tautomers of the nucleobases play fundamental roles in spontaneous mutations of DNA. Tautomers of neutral cytosine have been studied in the gas phase, but much less is known about charged species. Here, we report the observation and characterization of three tautomers of deprotonated cytosine anions, [trans-keto-amino-N3H-H8b] (tKAN3H8b- ), [cis-keto-amino-N3H-H8a] (cKAN3H8a- ) and [keto-amino-H] (KAN1- ), produced by electrospray ionization. Excited dipole-bound states (DBSs) are uncovered for the three anions by photodetachment spectroscopy. Excitations to selected DBS vibrational levels of cKAN3H8a- and tKAN3H8b- yield tautomer-specific resonant photoelectron spectra. The current study provides further insight into tautomerism of cytosine and suggests a new method to study the tautomers of nucleobases using electrospray ionization and anion spectroscopy.

Fluorescent enhancement of polyethyleneimine nano-polymers and the application in cellar imaging

Nano-polymers (NPs) with non-conjugated moiety emit bright fluorescence when irradiated by ultraviolet lights, which arouses extensive interests since they do not have traditional fluorophores or conjugated moieties. Although the mechanism was put forward in some reports and entitled as “crosslink enhanced emission” (CEE) the oxidation of starting material is also contributable for the enhanced fluorescence according to our researches. However this has been neglected until now. Herein, when aqueous solution of pure polyethyleneimine (PEI) was suffered from heating at 180° in air for 60 min crosslink of PEI molecules took place and produced PEI NPs. It emitted bright blue fluorescence and the quantum yield reached as high as 18.24% while PEI itself possessed none of fluorescence. Infrared, 1H nuclear magnetic resonance and X-ray photoelectron spectra disclosed the oxidation of PEI during the lasting heating. And the image of transmission electron microscope confirmed the production of PEI NPs. When PEI NPs were prepared in the presence of hydrogen peroxide they performed a successive enhancement of fluorescent intensity, which demonstrated the oxidation of PEI contributed a lot for the fluorescent enhancement of PEI NPs. Experimental results also demonstrated that the PEI NPs have a potential application in cellar imaging on account of the lower cytotoxicity and the reactivity to the activated folic acid.

Insight into the mechanism for photocatalytic degradation of ciprofloxacin with CeO2

CeO2 was found to be an efficient photocatalyst for the degradation of ciprofloxacin (CIP) under simulated solar light irradiation. The solution pH significantly affected the degradation efficiency and the optimized pH was in the range of 6–9. The scavenger experiment indicates that the photogenerated hole were the main active species for CIP degradation. The interaction between CIP and CeO2 was investigated by ultraviolet-visible diffuse reflectance, electron paramagnetic resonance and X-ray photoelectron spectra. The results demonstrate the electron transfer from the adsorbed CIP to CeO2. The activated CIP can be readily degraded by the holes. This suggests that the interaction between pollutants and photocatalyst plays an important role in pollutants removal. Finally, the intermediates were identified and a possible pathway for CIP degradation was proposed.

Comparison of Bonding Performance Between Plywood and Laminated Veneer Lumber Induced by High Voltage Electrostatic Field.

High voltage electrostatic field (HVEF) was applied in order to improve wood surface characteristics, bonding and mechanical properties of wood composites. Masson pine (Pinus massoniana Lamp.) plywood and laminated veneer lumber (LVL) were selected in this study. Surface characteristics were conducted by the electron spin resonance (ESR) and X-ray photoelectron spectra (XPS). Bonding interphase and mechanical properties were investigated by fluorescence microscopy and vertical density profile (VDP), bonding strength, wood failure ratio, MOE and MOR. The results indicated that more increments were obtained in free radicals, O/C ratios and C2-C4 components. This is because electrons broke more wood chemical groups and new ions occurred among wood surface under HVEF. Significantly decreased PF adhesive penetration depth (PD) and increased density at bonding interphase was achieved in HVEF treated composites. More decrease of PD and increment of density were observed in plywood than that of LVL. This was attributed to cross linked wood fibers among bonding interphase in plywood. Mechanical properties of bonding strength, wood failure ratio, MOE and MOR were significantly increased under HVEF treatment both for two composites. Higher bonding strength, MOE and MOR were obtained in plywood and their increments were as 98.53%, 33.33%, 18.55% and 12.72%.

Dipole-bound excited states and resonant photoelectron imaging of phenoxide and thiophenoxide anions.

We report photodetachment and resonant photoelectron-imaging studies of cryogenically cooled phenoxide (C6H5O-) and thiophenoxide (C6H5S-) anions. In a previous study [H. T. Liu et al. Angew. Chem., Int. Ed. 52, 8976 (2013)], a dipole-bound excited state was observed for C6H5O- at 97 cm-1 below the detachment threshold. Eight resonant photoelectron spectra were obtained via excitations to eight vibrational levels of the dipole-bound state (DBS) followed by autodetachment. Here we present a complete photodetachment spectrum of C6H5O- covering a spectral range 2600 cm-1 above the detachment threshold and revealing nine additional vibrational resonances of the DBS. We also report the first observation of a dipole-bound excited state for C6H5S-, 39 cm-1 below its detachment threshold of 18 982 cm-1. Photodetachment spectroscopy covering a spectral range 1500 cm-1 above the threshold reveals twelve vibrational resonances for the DBS of C6H5S-. By tuning the detachment laser to the vibrational resonances in the DBS of C6H5O- and C6H5S-, we obtain highly non-Franck-Condon resonant photoelectron spectra, as a result of mode-selectivity and the Δv = -1 propensity rule for vibrational autodetachment. Five new fundamental vibrational frequencies are obtained for the ground state of the C6H5O (X 2B1) radical. Intramolecular inelastic scattering is observed in some of the resonant photoelectron spectra, leading to the excitation of the Franck-Condon-inactive lowest-frequency bending mode (ν20) of C6H5O. The first excited state of C6H5O (A 2B2) is observed to be 0.953 eV above the ground state. Twelve resonant photoelectron spectra are obtained for C6H5S-, allowing the measurements of seven fundamental vibrational frequencies of the C6H5S radical, whereas the non-resonant photoelectron spectrum exhibits only a single Franck-Condon active mode. The current study again demonstrates that the combination of photodetachment spectroscopy and resonant photoelectron spectroscopy is a powerful technique to obtain vibrational information about polar radical species.

Conformation-selective resonant photoelectron imaging from dipole-bound states of cold 3-hydroxyphenoxide.

We report a photoelectron imaging and photodetachment study of cryogenically cooled 3-hydroxyphenoxide (3HOP) anions, m-HO(C6H4)O-. In a previous preliminary study, two conformations of the cold 3HOP anions with different dipole bound states were observed [D. L. Huang et al., J. Phys. Chem. Lett. 6, 2153 (2015)]. Five near-threshold vibrational resonances were revealed in the photodetachment spectrum from the dipole-bound excited states of the two conformations. Here, we report a more extensive investigation of the two conformers with observation of thirty above-threshold vibrational resonances in a wide spectral range between 18 850 and 19 920 cm-1 (∼1000 cm-1 above the detachment thresholds). By tuning the detachment laser to the vibrational resonances in the photodetachment spectrum, high-resolution conformation-selective resonant photoelectron images are obtained. Using information of the autodetachment channels and theoretical vibrational frequencies, we are able to assign the resonant peaks in the photodetachment spectrum: seventeen are assigned to vibrational levels of anti-3HOP, eight to syn-3HOP, and five to overlapping vibrational levels of both conformers. From the photodetachment spectrum and the conformation-selective resonant photoelectron spectra, we have obtained fourteen fundamental vibrational frequencies for the neutral syn- and anti-m-HO(C6H4)O⋅ radicals. The possibility to produce conformation-selected neutral beams using resonant photodetachment via dipole-bound excited states of anions is discussed.

Resonant photoelectron imaging of deprotonated uracil anion via vibrational levels of a dipole-bound excited state

We report both non-resonant and resonant high-resolution photoelectron imaging of cryogenically-cooled deprotonated uracil anions, N1[U-H]−, via vibrational levels of a dipole-bound excited state. Photodetachment spectroscopy of N1[U-H]− was reported previously (Liu et al., 2014), in which forty-six vibrational autodetachment resonances due to the excited dipole-bound state were observed. By tuning the detachment laser to the vibrational levels of the dipole-bound state, we obtained high-resolution resonant photoelectron spectra, which are highly non-Franck–Condon. The resonant photoelectron spectra reveal many Franck–Condon inactive vibrational modes, significantly expanding the capability of photoelectron spectroscopy. A total of twenty one fundamental vibrational frequencies for the N1[U-H] radical are obtained, including all eight low-frequency out-of-plane modes, which are forbidden in non-resonant photoelectron spectroscopy. Furthermore, the breakdown of the Δv=−1 propensity rule is observed for autodetachment from many vibrational levels of the dipole-bound state, due to anharmonic effects. In particular, we have observed intramolecular electron rescattering in a number of resonant photoelectron spectra, leading to excitations of low-frequency vibrational modes. Further theoretical study may be warranted, in light of the extensive experimental data and new observations, to provide further insight into the autodetachment dynamics and vibronic coupling in dipole-bound states, as well as electron molecule interactions.

Occupied and unoccupied electronic structures of an L-cysteine film studied by core-absorption and resonant photoelectron spectroscopies

Unoccupied and occupied electronic structures of an L-cysteine film have been studied by absorption and resonant photoelectron spectroscopies. Core absorptions at S-L, C-K, N-K, and O-K levels indicate that the lower unoccupied states are predominantly composed of oxygen-2p, carbon-2p, and sulfur-4s+3d orbitals, while higher unoccupied states may be attributed dominantly to nitrogen-np (n ≥ 3), oxygen-np (n ≥ 3), and sulfur-ns+md (n ≥ 4, m ≥ 3) orbitals. Resonant photoelectron spectra at S-L23 and O-K levels indicate that the highest occupied state is originated from sulfur-3sp orbitals, while oxygen-2sp orbitals contribute to the deeper valence states. The delocalization lifetimes of the oxygen-1s and sulfur-2p excited states are estimated from a core-hole clock method to be about 9 ± 1 and 125 ± 25 fs, respectively.