The electronic structure of 1,2,4,3-triazaphospholes: A study by UV photoelectron spectroscopy and ab intio molecular orbital methods

The UV photoelectron spectra of simple members of the 1H- and 2H-triazaphospholes are reported; the spectra were assigned by ab initio molecular-orbital configuration-interaction methods, following the observation of breakdown of Koopmanns' theorem at the SCF level. The ring electron distribution, and the implications for reactivity of the rings are discussed.     

Boron chelate complexes: X-ray and UV photoelectron spectra and electronic structure

Published data on the electronic structure of boron chelates are summarized for the first time. Ultraviolet photoelectron spectra of vapors, X-ray photoelectron spectra of molecular crystals, and results of modeling within the framework of the density functional theory are analyzed. Data on the effect of substituents on the electronic structure of complexes are systematized.     

Conformational properties and electronic structure of tetrahydrotetrazines studied by photoelectron spectroscopy and quantum chemical calculations

The photoelectron (PE) spectra of tetrahydro-1,2,3,4-tetrazines 1 and 2 and tetrahydro-1,2,4,5-tetrazines 3–5 have been recorded and their conformations have been investigated by ab initio SCF calculations. While v-tetrazine2 is planar, tetrazines 1 and 3–5 each possess two low-energy conformations, according to ab initio HF and Becke3LYP methods. Attempts to assign ionization potentials to molecular orbitals obtained by semiempirical PM3 calculations indicate that this method is not suited for the compounds studied. Best results were obtained when the ab initio hybrid method Becke3LYP of the density functional theory was employed. Two conformers of 1 and 3–5 are present in the gas phase and their PE spectra are superimposed one upon the other. For v-tetrazine1, ionizations arising from half-chair and unsymmetrical boat conformers have similar energies and cannot be separated in the PE spectrum. For s-tetrazine3, on the other hand, the spectrum clearly shows different ionizations of both half-chairs, 3ee and 3ae.     

Electronic structure and thermal decomposition of 5-methyltetrazole studied by UV photoelectron spectroscopy and theoretical calculations

The electronic properties and thermal decomposition of 5-methyltetrazole (5MTZ) are investigated using UV photoelectron spectroscopy (UVPES) and theoretical calculations. Simulated spectra of both 1H- and 2H-5MTZ, based on electron propagator methods, are produced in order to study the relative tautomer population. The thermal decomposition results are rationalized in terms of G2(MP2) results. 5MTZ yields a HOMO ionization energy of 10.82 ± 0.04 eV and the gas-phase 5MTZ assumes predominantly the 2H-form. Its gas-phase thermal decomposition starts at ca. 195 °C and leads to the formation of N₂,CH₃CN and HCN. N₂ is formed from two competing routes, involving 150.2 and 126.2 kJ/mol energy barriers, from 2H- and 1H-5MTZ, respectively. CH₃CN is formed also from two competing pathways, requiring activation energies of 218.3 (2H-5MTZ) and 198.6 kJ/mol (1H-5MTZ). Conclusions are also drawn in order to explain the formation of HCN from secondary reactions in the thermal decomposition process.     

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.     

Valence electronic structure of benzo-2,1,3-chalcogenadiazoles studied by photoelectron spectroscopy and density functional theory

The He I photoelectron spectra of benzo-2,1,3-thia-, selena-, and telluradiazole were measured, and the observed ionization bands were assigned by comparison with the results of DFT calculations. Whereas the B3LYP exchange-correlation functional provided orbital energies that permitted a preliminary assignment by application of Koopman's theorem, a more-accurate interpretation was established by calculation of the vertical ionization energies with the PW91 functional and analysis of the correlation of energy levels along the homologous series. This strategy clarified earlier disagreements in the assignment of the spectrum of benzo-2,1,3-thiadiazole.     

Wavelength dependence of electronic relaxation in isolated adenine using UV femtosecond time-resolved photoelectron spectroscopy

Electronic relaxation pathways in photoexcited nucleobases have received much theoretical and experimental attention due to their underlying importance to the UV photostability of these biomolecules. Multiple mechanisms with different energetic onsets have been proposed by ab initio calculations yet the majority of experiments to date have only probed the photophysics at a few selected excitation energies. We present femtosecond time-resolved photoelectron spectra (TRPES) of the DNA base adenine in a molecular beam at multiple excitation energies between 4.7-6.2 eV. The two-dimensional TRPES data is fit globally to extract lifetimes and decay associated spectra for unambiguous identification of states participating in the relaxation. Furthermore, the corresponding amplitude ratios are indicative of the relative importance of competing pathways. We adopt the following mechanism for the electronic relaxation of isolated adenine; initially the S(2)(ππ*) state is populated by all excitation wavelengths and decays quickly within 100 fs. For excitation energies below ～5.2 eV, the S(2)(ππ*)→S(1)(nπ*)→S(0) pathway dominates the deactivation process. The S(1)(nπ*)→S(0) lifetime (1032-700 fs) displays a trend toward shorter time constants with increasing excitation energy. On the basis of relative amplitude ratios, an additional relaxation channel is identified at excitation energies above 5.2 eV.     

X-ray and UV photoelectron spectroscopy of Ag nanoclusters

The main purpose of the present work is to analyze a series of Ag nanoparticles (NPs) with different size or ligand functionalization by using X-ray photoelectron spectroscopy (XPS) and to identify the differences in the band-shape and energy peak position of photoemission spectra due to the particle dimension. A transmission electron microscopy characterization was performed, to verify the consistency of the results. Three types of samples were prepared starting from AgNO₃ water solution and adding different capping agents. In the first two cases, the formation of NPs was promoted by the reduction of silver ions Ag⁺¹ to metallic Ag⁰ through the addition of sodium borohydride, whereas in the last case, it was triggered by the exposure to UV light. Depending on the size of the NPs, a different physical behavior can be recognized. NPs with diameter of about 5 nm are characterized by the phenomenon of localized surface plasmon resonance (LSPR). The other type of samples having a diameter of about 1.5 nm presents discrete energy levels instead of electronic bands, and in this case, a typical fluorescence phenomenon can be observed. In the latter case, we can refer to such systems as nanoclusters. The XPS analyses were focused on the Ag 3D spectra looking for the possible shifts of the Ag doublet as a function of the particles size. The ultraviolet photoelectron spectroscopy with He II source was used for the investigation of possible changes in the valence band.     

High-resolution UV photoelectron spectroscopy of diatomic halogens

Diatomic halogens are studied with UV photoelectron spectroscopy using new techniques to preserve high resolution even for reactive species. For the first time vibrational structure is observed on the ²Π_u,i (i = ^1/2,^3/2) states (F₂⁺, Cl₂⁺), the ²Σ_g⁺ states (F₂⁺, Cl₂⁺) and the Br₂⁺ (²Π_{u,$\text{3}\text{2}$}) state. On the ²Π_u,i states (F₂⁺, Cl₂⁺, Br₂⁺) spin-orbit splitting is resolved. Indications for a small potential barrier on the F₂⁺ (²Π_u,i) state for large internuclear distances are found. A new value for the spin-orbit splitting of the Cl₂⁺(²Π_g) state is presented (= ?725 cm^?1). The complementary nature of optical emission and photoelectron spectroscopy for small ions is demonstrated leading to a more complete picture of the F₂⁺ (²Π_u,i) and Cl₂⁺ (²Π_u,i) ionic states.     

Study of electronic structure of certain phenazasilines by quantum chemistry and UV spectroscopy methods

A spectroscopic and quantum-chemical investigation of heterocyclic derivatives of 9,10-dihydroanthracene, viz., phenazasilines EtN(C₆H₄)₂SiMe₂ (I), MeN(C₆H₄)₂SiMe₂ (II), and EtN(C₆H₄)₂SiHME (III), was carried out. The experimental absorption spectra were theoretically interpreted by calculating the electronic structure of the molecules by the CNDO/S3 method, whose system of semiempirical parameters was supplemented by the silicon parameters. The nonplanar structure of the phenazasiline heterocyclic ring and the presence of two butterfly type conformations in the molecule of III was taken into account. The calculated bond lengths and oscillator forces of the electronic transitions agree well with the UV spectroscopy data and the photoelectronic spectrum of the molecule of II. The polarization spectra of phenazasilines I–III were predicted.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 2, pp. 229–232, March–April, 1985.     

Conformational analysis of alkyl aryl ethers and alkyl aryl sulphides by photoelectron spectroscopy

Photoelectron spectroscopy shows that in t-butoxybenzenes, but not in methoxy-, ethoxy- or isopropoxybenzenes, there is a loss of p-π orbital overlap. A similar effect is observed in 2,6-dimethylalkoxybenzenes. In alkyl aryl sulphides two conformers predominate, the one with maximum p-π overlap and the other with reduced overlap. The importance of the less conjugated conformer increases monotonously through the series hydrogen, methyl, ethyl, isopropyl and t-butyl in alkyl phenyl sulphides.     

Valence-band electronic structure of iron phthalocyanine: an experimental and theoretical photoelectron spectroscopy study

The electronic structure of iron phthalocyanine (FePc) in the valence region was examined within a joint theoretical-experimental collaboration. Particular emphasis was placed on the determination of the energy position of the Fe 3d levels in proximity of the highest occupied molecular orbital (HOMO). Photoelectron spectroscopy (PES) measurements were performed on FePc in gas phase at several photon energies in the interval between 21 and 150 eV. Significant variations of the relative intensities were observed, indicating a different elemental and atomic orbital composition of the highest lying spectral features. The electronic structure of a single FePc molecule was first computed by quantum chemical calculations by means of density functional theory (DFT). The hybrid Becke 3-parameter, Lee, Yang and Parr (B3LYP) functional and the semilocal 1996 functional of Perdew, Burke and Ernzerhof (PBE) of the generalized gradient approximation (GGA-)type, exchange-correlation functionals were used. The DFT/B3LYP calculations find that the HOMO is a doubly occupied π-type orbital formed by the carbon 2p electrons, and the HOMO-1 is a mixing of carbon 2p and iron 3d electrons. In contrast, the DFT/PBE calculations find an iron 3d contribution in the HOMO. The experimental photoelectron spectra of the valence band taken at different energies were simulated by means of the Gelius model, taking into account the atomic subshell photoionization cross sections. Moreover, calculations of the electronic structure of FePc using the GGA+U method were performed, where the strong correlations of the Fe 3d electronic states were incorporated through the Hubbard model. Through a comparison with our quantum chemical calculations we find that the best agreement with the experimental results is obtained for a U(eff) value of 5 eV.     

Structural and electronic characterization of self-assembled molecular nanoarchitectures by X-ray photoelectron spectroscopy

Molecular monolayers and similar nanoarchitectures are indicative of the promising future of nanotechnology. Therefore, many scientists recently devoted their efforts to the synthesis, characterization, and properties of mono- and multilayer-based systems. In this context, X-ray photoelectron spectroscopy is an important technique for the in-depth chemical and structural characterization of nanoscopic systems. In fact, it is a surface technique suitable for probing thicknesses of the same order of the photoelectron inelastic mean free paths (a few tens of ångströms) and allows one to immediately obtain qualitative and quantitative data, film thickness, surface coverage, molecule footprint, oxidation states, and presence of functional groups. Nevertheless, other techniques are important in obtaining a complete spectroscopic characterization of the investigated systems. Therefore, in the present review we report on X-ray photoelectron spectroscopy of self-assembled molecular mono- and multilayer materials including some examples on which other characterization techniques produced important results.

Gas phase analogs of stable sodium-tin Zintl ions: anion photoelectron spectroscopy and electronic structure

Mass spectrometry and photoelectron spectroscopy together with first principles theoretical calculations have been used to study the electronic and geometric properties of the following sodium-tin, cluster anion/neutral cluster combinations, (Na(n)Sn(4))(-)/(Na(n)Sn(4)), n = 0-4 and (NaSn(m))(-)/(NaSn(m)), m = 4-7. These synergistic studies found that specific Zintl anions, which are known to occur in condensed Zintl phases, also exist as stable moieties within free clusters. In particular, the cluster anion, (Na(3)Sn(4))(-) is very stable and is characterized as (Na(+))(3)(Sn(4))(-4); its moiety, (Sn(4))(-4) is a classic example of a Zintl anion. In addition, the cluster anion, (NaSn(5))(-) was the most abundant species to be observed in our mass spectrum, and it is characterized as Na(+)(Sn(5))(2-). Its moiety, (Sn(5))(2-) is also known to be present as a Zintl anion in condensed phases.