Electronic states of tetrahydrofuran molecules studied by electron collisions

Electronic states of tetrahydrofuran molecules were studied in the excitation energy range 5.5-10 eV using the technique of electron energy loss spectroscopy in the gas phase. Excitation from the two conformations, C(2) and C(s), of the ground state of the molecule are observed in the measured energy loss spectra. The vertical excitation energies of the (3)(n(o)3s) triplet state from the C(2) and C(s) conformations of the ground state of the molecule are determined to be 6.03 ± 0.02 and 6.25 ± 0.02 eV, respectively. The singlet-triplet energy splitting for the n(o)3s configuration is determined to be 0.31 eV. It is also found that excitation from the C(s) conformation of the ground state has a higher cross section than that from the C(2) conformation.     

Excited electronic states of the fluorobenzenes by variable angle electron impact spectroscopy

Electron-impact excitation spectra of benzene, fluorobenzene, o-difluorobenzene, 1,3,5-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, pentafluorobenzene, and hexafluorobenzene have been measured at impact energies of 50 eV and either 25 eV or 30 eV, and scattering angles from 5° to 80°. Each molecule shows an absorption maximum at about 3.9 eV corresponding to a singlet → triplet, π → π^*, transition. In benzene, fluorobenzene, o-difluorobenzene, and 1,3,5-trifluorobenzene, an additional singlet → triplet transition was detected at about 5.6 eV. Three singlet → singlet transitions analogous to the 4.90, 6.20, and 6.95 eV transitions in benzene are seen in each of the fluorine-substituted molecules. The more highly substituted compounds exhibit an additional singlet → singlet transition that is most clearly observed in the hexafluorobenzene spectrum with a peak at 5.32 eV.     

Excitation of He(31 D) by electron impact

We report new results of the Stokes parametersP ₁ toP ₄ and of the coherence parametersP _lin, γ _a , ρ₀₀ andL _∝ for He(3¹ D) excitation by electron impact in the energy range 40 eV to 81.6 eV obtained by the scattered electron-polarized photon coincidence technique. The present results are, where available, in fair agreement with previous measurements of other groups but disagree with the available calculations based on different models.     

Triplet states in the dissociative excitation of water by electron impact

The electron-impact excitation of water has been reinvestigated over the energy range 9–180 eV. Energy-dependent pressure effects have been observed. It is suggested that these are due to production of one or more triplet states of water which undergo collisionally assisted predissociation. Threshold energies for these processes have been determined.     

Vibrational and electronic excitation in p-benzoquinone by electron impact

Vibrational and electronic excitation by electron impact in p-benzoquinone was studied using a trochoidal electron spectrometer. Two distinct patterns of vibrational excitation were observed. First, low quanta of a few selected vibrations are specifically excited at incident electron energies corresponding to shape resonances. Some resonances excite mainly the CO stretch, others the CH stretch vibration, and this selectivity is used in the discussion of the assignment of the resonances. A second pattern is an unspecific excitation of a quasi-continuum where no structure due to individual vibrational levels can be discerned. This feature peaks at threshold, large amounts of vibrational energy can be deposited in the molecule, and the excitation also proceeds via shape resonances. Electronic excitation spectra in the valence and Rydberg regions are also presented and discussed. A band observed at 4.37 eV with low residual energies has been tentatively assigned to the second π — π* triplet state ³B_3g.     

Cleavage of the ether bond by electron impact: differences between linear ethers and tetrahydrofuran

Dissociative electron attachment (DEA) to diethyl ether yielded primarily the C(2)H(5)O(-) ion, with a strong Feshbach resonance band at 9.1 eV and a weaker shape resonance band at 3.89 eV. Very similar spectra were obtained for dibutyl ether, with C(4)H(9)O(-) bands at 8.0 and 3.6 eV. Some of these primary ions subsequently lost H(2) and yielded weaker signals of the C(2)H(3)O(-) and C(4)H(7)O(-) ions. In contrast, DEA to the cyclic ether tetrahydrofuran (THF) yielded mainly a fragment of mass 41, presumably deprotonated ketene, at 7.65 eV. The low-energy band was missing in THF. H(-) with two bands at 6.88 and 8.61 eV, and an ion of mass 43 (presumably deprotonated acetaldehyde) with two bands at 6.7 and 8.50 eV were also observed. We propose that in the primary DEA step the C-O bond is cleaved in both the open-chain and the cyclic ethers. In the open-chain ethers the excess energy is partitioned between the (internal and kinetic) energies of two fragments, resulting in an RO(-) ion cool enough to be observed. The CH(2)(CH(2))(3)O(-) ion resulting from cleavage of the C-O bond in THF contains the entire excess energy (more than 6 eV at an electron energy of 7.65 eV) and is too short-lived with respect to further dissociation and thermal autodetachment to be detected in a mass spectrometer. These findings imply that there could be a substantial difference between the fragmentation in the gas phase described here and fragmentation in the condensed phase where the initially formed fragments can be rapidly cooled by the environment.     

Absolute cross sections for electronic excitations of cytosine by low energy electron impact

The absolute cross sections (CSs) for electronic excitations of cytosine by electron impact between 5 and 18 eV were measured by electron-energy-loss (EEL) spectroscopy of the molecule deposited at low coverage on an inert Ar substrate. The lowest EEL features found at 3.55 and 4.02 eV are ascribed to transitions from the ground state to the two lowest triplet 1?(3)A(')(π→π(?)) and 2?(3)A(')(π→π(?)) valence states of the molecule. Their energy dependent CSs exhibit essentially a common maximum at about 6 eV with a value of 1.84×10(-17)?cm(2) for the former and 4.94×10(-17)?cm(2) for the latter. In contrast, the CS for the next EEL feature at 4.65 eV, which is ascribed to the optically allowed transition to the 2?(1)A(')(π→π(?)) valence state, shows only a steep rise to about 1.04×10(-16)?cm(2) followed by a monotonous decrease with the incident electron energy. The higher EEL features at 5.39, 6.18, 6.83, and 7.55 eV are assigned to the excitations of the 3?(3,1)A(')(π→π(?)), 4?(1)A(')(π→π(?)), 5?(1)A(')(π→π(?)), and 6?(1)A(')(π→π(?)) valence states, respectively. The CSs for the 3?(3,1)A(') and 4?(1)A(') states exhibit a common enhancement at about 10 eV superimposed on a more or less a steep rise, reaching, respectively, a maximum of 1.27 and 1.79×10(-16)?cm(2), followed by a monotonous decrease. This latter enhancement and the maximum seen at about 6 eV in the lowest triplet states correspond to the core-excited electron resonances that have been found by dissociative electron attachment experiments with cytosine in the gas phase. The weak EEL feature found at 5.01 eV with a maximum CS of 3.8×10(-18)?cm(2) near its excitation threshold is attributed to transitions from the ground state to the 1?(3,1)A(")(n→π(?)) states. The monotonous rise of the EEL signal above 8 eV is attributed to the ionization of the molecule. It is partitioned into four excitation energy regions at about 8.55, 9.21, 9.83, and 11.53 eV, which correspond closely to the ionization energies of the four highest occupied molecular orbitals of cytosine. The sum of the ionization CS for these four excitation regions reaches a maximum of 8.1×10(-16)?cm(2) at the incident energy of 13 eV.     

Experimental and theoretical electron momentum spectroscopic study of the valence electronic structure of tetrahydrofuran under pseudorotation

The most populated structure of tetrahydrofuran (THF) has been investigated in our previous study using electron momentum spectroscopy (EMS). Because of the relatively low impact energy (600 eV) and low energy resolution (DeltaE = 1.20 eV) in the previous experiment, only the highest occupied molecular orbital (HOMO) of THF was investigated. The present study reports the most recent high-resolution EMS of THF in the valence space for the first time. The binding energy spectra of THF are measured at 1200 and 2400 eV plus the binding energies, respectively, for a series of azimuthal angles. The experimentally obtained binding energy spectra and orbital momentum distributions (MDs) are employed to study the orbital responses of the pseudorotation motion of THF. The outer valence Greens function (OVGF), the OVGF/6-311++G** model, and density function theory (DFT)-based SAOP/et-pVQZ model are employed to simulate the binding energy spectra. The orbital momentum distributions (MDs) are produced using the DFT-based B3LYP/aug-cc-pVTZ model, incorporating thermodynamic population analysis. Good agreement between theory and experiment is achieved. Orbital MDs of valence orbitals exhibit only slight differences with respect to the impact energies at 1200 and 2400 eV, indicating validation of the plane wave impulse approximation (PWIA). The present study has further discovered that the orbital MDs of the HOMO in the low-momentum region (p < 0.70 a.u) change significantly with the pseudorotation angle, phi, giving a v-shaped cross section, whereas the innermost valence orbital of THF does not vary with pseudorotation, revealing a very different bonding mechanism from the HOMO. The present study explores an innovative approach to study pseudorotation of sugar puckering, which sheds a light to study other biological systems with low energy barriers among ring-puckering conformations.     

Stabilisation of spin-singlet electronic states in transition metal clusters with a delocalised electron pair

A model is proposed for the interpretation of magnetic properties of polynuclear mixed-valence complexes containing a pair of delocalised electrons. It is shown that in many cases the delocalisation leads to a spin-singlet ground state of clusters. The combined delocalisation + vibronic mechanism of stabilisation of the spin-singlet state is proposed for clusters containing triangles of metal atoms.     

All electron ab initio investigations of the electronic states of the MoN molecule

The low lying electronic states of the molecule MoN were investigated by performing all electron ab initio multi-configuration self-consistent-field (CASSCF) calculations. The relativistic corrections for the one electron Darwin contact term and the relativistic mass-velocity correction were determined in perturbation calculations. The electronic ground state is confirmed as being ⁴∑⁻. The chemical bond of MoN has a triple bond character because of the approximately fully occupied delocalized bonding π and σ orbitals. The spectroscopic constants for the ground state and ten excited states were derived. The excited doublet states ²∑⁻, ²Γ, ²Δ, and ²∑⁺ are found to be lower lying than the ⁴Π state that was investigated experimentally. Elaborate multi-configuration configuration-interaction (MRCI) calculations were carried out for the states ⁴∑⁻ and ⁴∏ using various basis sets. The spectroscopic constants for the ⁴∑⁻ ground state were determined as r_e=1.636 Å and ω_e=1109 cm⁻¹, and for the ⁴∏ state as r_e=1.662 Å and ω_e=941 cm⁻¹. The values for the ground state are in excellent agreement with available experimental data. The MoN molecule is polar with a charge transfer from Mo to N. The dipole moment was determined as 2.11 D in the ⁴∑⁻ state and as 4.60 D in the ⁴∏ state. These values agree well with the revised experimental values determined from molecular Stark spectroscopic measurements. The dissociation energy, D_e, is determined as 5.17 eV, and D₀ as 5.10 eV.     

Study of electron states of solids by techniques of electron spectroscopy

Studies of valence bands and core levels of solids by photoelectron spectroscopy are described at length. Satellite phenomena in the core level spectra have been discussed in some detail and it has been pointed out that the intensity of satellites appearing next to metal and ligand core levels critically depends on the metal-ligand overlap. Use of photoelectron spectroscopy in investigating metal-insulator transitions and spin-state transitions in solids is examined. It is shown that relative intensities of metal Auger lines in transition metal oxides and other systems provide valuable information on the valence bands. Occurrence of interatomic Auger transitions in competition with intraatomic transitions is discussed. Applications of electron energy loss spectroscopy and other techniques of electron spectroscopy in the study of gas-solid interactions are briefly presented.     

Investigation of low-lying electronic states in nitromethane by electron-impact spectroscopy

Low energy, variable angle, electron-impact energy-loss spectra of nitromethane have been obtained. A previously unreported singlet → triplet excitation with maximum intensity at 3.8 eV energy loss is observed and its relevance to the gas phase photochemistry of nitromethane is discussed. An additional weak transition with maximum intensity at 4.45 eV energy loss is tentatively assigned to a symmetry-forbidden transition.     

Excitation of degenerate vibrations in non-degenerate electronic bands

The vibrational rule structuic of the 2A'₁ band in the photoelectron spectrum of BF₃ is analyzed Using ab initio calculated coupling constants, It is shown that some lines of this spectrum represent excitation of single quanta of the degenerate stretching vibration They borrow their intensity from the adjacent 2E' state via a pseudo-Jahn-Teller interaction     

Dissociation of ethane by electron impact

The absolute total dissociation cross section for ethane is reported for electron energies between 10 and 600 eV. A maximum value of 7.6 × 10^?16 cm² occurs at 80 eV while the apparent threshold is ≈ 10 eV. Dissociative ionization is more probable than dissociation into neutral fragments at all energies except in the threshold region. The data indicates that fragmentation involving methane elimination (c^? + C₂ H₆ → e^? + CH₄ + CH₂) occurs in less than 2% of the dissociative events for 50 < E < 600 eV. Arguments are presented which suggest that some of the lower excited states of ethane are stable against dissociation.     

Triplet states of ketene by trapped electron spectroscopy

The threshold electron impact excitation spectrum of ketene is reported. The spectrum is interpreted in comparison with results of an ab initio frozen core calculation. Triplet states (³A₂, ³A₁, ³B₁) are observed at 3.8, 5.0 and 5.8 eV excitation energy.     

Excitation to symmetry forbidden vibronic levels in the 1B2u state by controlled electron impact on benzene

The ¹B_2u-¹A_1g fluorescence emission of benzene excited by controlled electron impact was measured in the 14 – 100 eV region. The optically forbidden 6° levels were preferentially, excited. This indicates that a non-dipole transition takes place under low-energy electron-molecule collisions.     

Low-energy electronic states of methylene

Ab initio SCF calculations using a slightly extended basis set have been carried out on the low-energy electronic states of methylene. The equilibrium geometries and energies of these states are determined, and potential curves for each state are obtained.     

Excited electronic states of NiCO

The results of ab initio SCF and CI calculations on the electronic states of NiCO are reported. The ¹Σ⁺ ground state is a mixture of two primary configurations associated with the Ni 3d¹⁰ and 3d⁹4s states, and is bound by 18 kcal mol⁻¹ with respect to Ni and CO at r_nic =1.77 Å. The excited states (within 22000 cm⁻¹ of the ground state) can be divided into a lower manifold, principally involving the Ni(3d⁹4s) electronic configuration, and a higher manifold, formally associated with the charge transfer configuration Ni⁺ (3d⁹)CO⁻ (π1).     

The electronic states of biacetyl

The ordering of the lower electronic states of biacetyl is discussed and the consequences for the mechanism of the radiationless S → T transitions are considered in detail.