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Two model humic compounds, 2,6- and 2,5-dihydroxyacetophenone, were investigated by negative ion mass spectrometry. Dissociative electron attachment cross-sections and negative ion autodetachment lifetimes were measured in the electron energy region 0–10 eV. Adiabatic electron affinities of the compounds under investigation were evaluated. The results obtained were rationalized using DFT B3LYP/6-31G+(d) quantum-chemical calculations.

Cycloheptatriene derivatives are studied by means of resonance electron capture negative ion mass spectrometry (REC NIMS). The average lifetimes of molecular negative ions (NIs) are measured with respect to electron autodetachment. Using the Arrhenius approach, electron affinity EAa of the molecules under study is estimated, and the effective temperature of the resulting negative molecular ions is determined as a function of the electron energy. It is assumed that the dissociation of negative molecular ions in the ground electronic state is a process similar to that of the thermal degradation of molecules.

Resonance attachment of low-energy (0–14 eV) electrons to a series of natural polyphenolic naphthoquinones (so-called spinochromes) derived from sea urchins is studied by means of dissociative electron attachment (DEA) spectroscopy. The experimental findings are interpreted using quantum-chemical calculations of the empty level structure to predict the energies of negative ion resonant states as well as the thermodynamic energy thresholds for formation of fragments by DEA. A variety of fragment species is found to be formed at very low energies of incident electrons, thus modeling reductive conditions in living cells near the pathways of cellular electron transfer. In particular, the temporary molecular anions of the compounds under investigation dissociate efficiently through elimination of neutral H atoms or diatomic hydrogen molecules (in analogy with previous findings in flavonoids), this process being energetically possible owing to the presence of multiple hydroxyl groups usually associated with radical scavenging activity. A likely correlation between dehydrogenation of spinochromes stimulated by electron attachment and their well-documented antioxidant protective properties is briefly discussed.

A possible correlation between electron acceptor properties, in particular, dissociative electron attachment (DEA) and biological activity for a series of xenobiotic species (organic pollutants, polyphenolic antioxidants, and ascorbic acid) is reported. Formation and decay of temporary negative ions (TNIs) are studied using electron transmission and DEA spectroscopies. Experimental findings are assigned with the support of density functional theory calculations and are discussed in connection with the effects produced by these compounds in living cells. The basic ideas of the present study are derived from the work published in the earlier 60th of the XX century by A. Szent-Györgyi [1,2] and J. Lovelock [3]. Likely sources of electrons able to interact with xenobiotic molecules to form TNIs under cellular conditions are tentatively associated with mitochondria and cytochrome P450 enzymes. The formed TNIs are supposed to decay via the DEA mechanism producing negatively charged and neutral fragments, in analogy with those observed by DEA spectroscopy under gas-phase conditions. Electrochemical studies of reductive dehalogenation [4] and dehydrogenation [5] in solution demonstrate that TNIs can dissociate in condensed environment instead of dissipating their excess energy. Preliminary conclusions about a correlation between DEA and biochemical processes are summarized.

The energies of formation and dissociative decays of temporary negative ions of the organophosphorus insecticide chlorpyrifos (CPF) are studied using electron transmission spectroscopy (ETS), dissociative electron attachment spectroscopy (DEAS) and quantum-chemical calculations. Three features are displayed by ETS at 2.4, 3.1 and 4.30 eV, which are ascribed to empty σ* MOs, a higher-lying π* MO and a core-excited state, respectively. Two stable π* anion states are predicted by the calculations. Most of the negative fragments are detected by DEAS at thermal energies of the incident electrons, being thus associated with the dissociation of stable (vibrationally excited) negative ion states formed by electron attachment into the π* LUMO and LUMO+1. The CPF− molecular anions (not observed in the present study) are expected to decay by fast dissociation to give the most abundant ([CPF – HCl]−) species, which in turn dissociates on the microsecond timescale, producing as much as six metastable peaks in the mass spectrum. The m/z = 196 and 169 negative fragments, structurally similar to the main metabolites of CPF, 3,5,6-trichloro-2-pyridinol and O,O-diethyl thiophosphate, respectively, are formed by the direct decomposition of CPF−. Active radicals able to abstract hydrogen atoms from lipid membranes are generated as neutral counterparts of the observed anion fragments. A likely involvement of DEA in the biotransformation of CPF by cytochrome P450 enzymes in a reductive environment producing toxic species and precursors of the main metabolites is briefly discussed.

We have studied low energy electron attachment to a series of alcohols with one/two chlorine atoms. We have applied two experimental methods: the electron swarm (SWARM) and negative ion mass spectrometry (NIMS). The electron attachment processes in the mixtures of chloroalcohols with carbon dioxide have been investigated using an electron swarm technique. We obtained rate coefficients ( k 's) and the activation energies ( E a 's) for CH 2 ClCH 2 OH, CH 2 ClCH 2 CH 2 OH, CH 2 ClCH(OH)CH 2 Cl, CH 2 ClCHClCH 2 OH and CH 2 ClCH(OH)CH 2 OH in the temperature range 298–378 K. The negative ion mass spectra of CH 2 ClCH 2 OH, CH 2 ClCH 2 CH 2 OH, CH 2 ClCH(OH)CH 2 Cl and CH 2 ClCH(OH)CH 2 OH has been investigated. The anion yields were measured in the electron energy range 0–15 eV.

A number of compounds related to quinone derivatives is investigated by means of density functional theory in the B3LYP/6-31G(d) mode. Vertical electron affinity E va and/or electron affinity E a for the investigated compounds are known from experiments. The correlation between the calculated energies of π* molecular orbitals with the E va values measured via electron transmission spectroscopy is determined with a coefficient of 0.96. It is established that theoretical values of the adiabatic electron affinity, calculated as the difference between the total energies of a neutral molecule and a radical anion, correlate with E a values determined from electron transfer experiments with a correlation coefficient of 0.996.

The temperature dependence of the mean lifetime of Ph-N=N-Ph− azobenzene negative molecular ions on the captured electron energy is studied with a static mass spectrometer by the method of resonance electron capture. A family of respective experimental dependences is calculated accurate to 2–10%. It is shown that the molecular anions in the epithermal electron energy range can be stabilized through internal conversion, namely, a series of fast radiationless transitions without change in the multiplicity.

RATIONALE: Electron Affinity (EA) is one of the fundamental properties of a molecule. EA values can be measured with various experimental methods, although their availability is still relatively limited. We make an attempt to use Dissociative Electron Attachment Spectroscopy (DEAS) data for evaluation of the EAs of twelve naphthoquinone (NQ) derivatives. METHODS: Naphthoquinone (NQ) and eleven of its hydroxyl derivatives were investigated by means of DEAS. A combined investigation of NQ and juglone by means of the Electron Transmission Spectroscopy (ETS) and DEAS techniques, with the support of density functional theory (DFT) calculations, allowed us to elucidate the empty-level structures of NQ and its hydroxyl derivatives. RESULTS: All molecules under investigation form extremely long-lived molecular anions associated with three resonant states (except for NQ, where only two long-lived resonances were observed). The hydroxyl substituents of NQ cause an increase in EA and number of internal degrees of freedom (N), and, as a result, an increase in the mean electron autodetachment lifetimes of the molecular negative ions (NIs). Evaluation of the EAs from the measured lifetimes of the molecular NIs through a simple Arrhenius approximation gives results in reasonable agreement with those obtained with DFT calculations. CONCLUSIONS: NI lifetime measurements by means of a modified DEAS instrumentation can provide quantitative data of EA. A simple Arrhenius approximation seems to be adequate to describe the process of electron detachment from molecular anions. Copyright © 2014 John Wiley & Sons, Ltd.

A series of quinone derivatives with experimentally determined energies of vertical electron capture (Eva) and (or) adiabatic electron affinities (Ea) are studied by density functional theory on the DFT/B3LYP/6-31G(d) level. The calculated π*-MO energies are linearly correlated with the Eva values measured by electron transmission spectroscopy and the Ea values known from the electron transfer experiment with a correlation coefficient of 0.997. The adiabatic affinities Ea of quinone derivatives can be evaluated with acceptable accuracy by the B3LYP/6-31G(d) method using a scaling procedure with the shift.

Processes resulting in the formation of negative ions by molecules of some diterpene alkaloids via resonance electron capture have been studied. The mass spectra of these compounds have a small number of lines represented largely by intense peaks in the thermal electron energy region and are due to electron capture onto the lower unoccupied molecular orbital, which is π*-C=O or π*-Ph-C=O in character.

The dissociative capture of slow electrons by tetrachlorethylene (C2Cl4) has been investigated by resonant electron capture negative ion mass spectrometry. Metastable ions with fractional mass numbers 7.5, 17.5, and 19 corresponding to the C2Cl4− → Cl− + C2Cl3 and Cl2− → Cl− + Cl decays occurring at the microsecond timescale have been detected. It has been revealed that Cl2− anions, which are fragment ions, can dissociate at the microsecond timescale, which is very surprising for a system with one internal degree of freedom. This process is assumingly attributed to the rotational excitation of Cl2− anions. Thus, the experimental estimate of the time of rovibronic relaxation in the Cl2− anion has been obtained.

Experimental data obtained using electron transmission spectroscopy and negative ion mass spectrometry based on resonance electron capture are interpreted within the framework of a spherical potential well model in application to a series of chloro-and bromoalkane molecules. Allowance for the scattering of a single partial p-wave of the incoming electron makes possible (i) reproduction of the ratio of a resonance peak width to the electron energy observed in the electron transmission spectra and (ii) establishment of a relation between the total cross section of electron scattering on a molecule and the dissociative electron attachment cross section. The proposed model offers a radical simplification of the approach developed previously based on the Fashbach-Fano resonance theory.

Phthalide, the simplest chain of conductive polymer thin film, was investigated by means of Electron Transmission Spectroscopy, Negative Ion Mass Spectrometry, and density functional theory quantum chemistry. It has been found that formation of gas-phase long-lived molecular anions of phthalide around 0.7 eV takes place through cleavage of a C–O bond of the pentacyclic ring of the parent molecular anion to give a vibrationally excited (electronically more stable) open-ring molecular anion. The energy of the transition state for ring opening of the parent negative ion is calculated to be 0.65 eV above the neutral ground state of the molecule. The energy (2.64 eV) evaluated for the corresponding transition state in the neutral molecule is much higher, so that the process of electron detachment from the anion must lead to a neutral molecule with its initial pentacyclic structure. The average lifetime of the molecular negative ions formed at an electron energy of 0.75 eV and 80 °C is measured to be about 100 μs. The known switching effect of thin phthalide films could stem from the presence of a similar open/closed transition state also in the polymer.

Adiabatic Electron Affinity (EAa) is one of the fundamental properties of a molecule. EA values can be measured with various experimental methods, although their availability is still relatively limited. Here we extend our evaluations of EAas using Negative Ion Mass Spectrometry (NIMS). A series of eleven nitrobenzene derivatives were investigated by means of NIMS. The mean autodetachment lifetimes of molecular anions were measured. Vertical and adiabatic EAs were also estimated using DFT calculations. For the compounds under investigation, the EAas evaluated from the measured anion lifetimes, assuming a simple Arrhenius approximation, are in good agreement with the corresponding experimental values. It is shown that the pre-exponential frequency factor (typical time of the anion motion on the reaction coordinate) is of the order of magnitude of 500 fs.

Three mono-substituted and six poly-substituted haloalkanes derivatives were investigated by means of negative ion mass spectrometry (NIMS). Available electron transmission spectroscopy (ETS) data were used for the treatment of NIMS results. Comparison of the ETS spectra of mono-substituted bromo- and chloroalkanes show that these families of compounds exhibit similar regularities in the process of NI formation. Capture of the p-partial wave dominates in the lowest anion state formation. In the series of mono-substituted bromo- and chloroalkanes the energy difference (Shift) between the vertical attachment energy (VAE) in ETS spectra and the maximum of the NI formation in dissociative electron attachment (DEA) spectra correlates approximately linearly with the VAE value for the given molecule. The slopes of these dependencies are different for the mono-substituted chloro and bromo derivatives. It is conjectured that, in the derivatives di-substituted in the 1,2-positions, there is a shallow minimum in the repulsive anion potential curve, which makes possible temporary trapping of the anion. This delay is long enough for the rearrangement process and formation of the Hal2- ions. This effect is not detected in 1,1-halogenated derivatives.

Temperature dependence of the mean autodetachment lifetime in the gas phase of the molecular negative ion (MNI) of the p -benzoquinone (PBQ) molecule was measured by means of electron capture negative ion mass spectrometry (ECNI MS). The energy of the maximum of C 6 H 4 O 2 − formation shifts monotonically from 1.35 to 1.16 eV as the temperature is raised from 348 to 568 K. Simultaneously, the mean autodetachment lifetime τ a of this MNI decreases from 41 to 24 μs.

A model proposed for describing the scattering of low-energy electrons (whose energy ranges between thermal energy and several electronvolts) from polyatomic molecules makes it possible to estimate the lifetime of shape resonances. The parameters of the model are determined by specific structural and experimental characteristics of molecules. The results of approximate computations of the lifetimes for negative ions of molecules with different symmetries (diatomic halogens, parabenzoquinone, fullerene C60, benzothiadiazoles, anthraquinone derivatives, and substituted benzene forms) are presented. The obtained data show that the lifetimes are sufficient for the formation of fragment ions observed in the mass spectra of negative ions.

Electron Affinity (EA) is one of the fundamental properties of a molecule. EA values can be measured with various experimental methods, although their availability is still relatively limited. We make an attempt to use Dissociative Electron Attachment Spectroscopy (DEAS) data for evaluation of the EAs of twelve naphthoquinone (NQ) derivatives.Naphthoquinone (NQ) and eleven of its hydroxyl derivatives were investigated by means of DEAS. A combined investigation of NQ and juglone by means of the Electron Transmission Spectroscopy (ETS) and DEAS techniques, with the support of density functional theory (DFT) calculations, allowed us to elucidate the empty-level structures of NQ and its hydroxyl derivatives.All molecules under investigation form extremely long-lived molecular anions associated with three resonant states (except for NQ, where only two long-lived resonances were observed). The hydroxyl substituents of NQ cause an increase in EA and number of internal degrees of freedom (N), and, as a result, an increase in the mean electron autodetachment lifetimes of the molecular negative ions (NIs). Evaluation of the EAs from the measured lifetimes of the molecular NIs through a simple Arrhenius approximation gives results in reasonable agreement with those obtained with DFT calculations.NI lifetime measurements by means of a modified DEAS instrumentation can provide quantitative data of EA. A simple Arrhenius approximation seems to be adequate to describe the process of electron detachment from molecular anions.

A series of benzene derivatives (R(1)C(6)H(4)R(2)) has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), and PM3 quantum chemical calculations. The dissociation channel M(-.) --> Hal(-) + (M - Hal). is analysed from the point of view of symmetry conservation. Generally, a symmetry ban on dissociation may be avoided in at least two ways: (i) out-of-plane vibrations of the halogen atom in the molecular negative ion (MNI), mixing pi- and sigma-states of the anion; (ii) symmetrical in-plane vibration of the C-Hal bond, changing the order of the empty levels in the MNI with subsequent radiationless conversion into a sigma-state. Our analysis shows that neither of them provides a satisfactory explanation of the ECNI mass spectra for chlorobenzene, if one retains the usual assumption that an additional electron goes into the LUMO of the neutral molecule. Thus, it may be concluded that in this case electron capture causes a significant perturbation of the energy ordering of vacant orbitals, thus making the frozen shell approximation inapplicable. Copyright 2000 John Wiley & Sons, Ltd.

A series of halogenated anthraquinone (AQ) derivatives has been studied by means of electron capture negative ion (NI) mass spectrometry (ECNI-MS). 1Cl-AQ and 2Br-AQ display dramatically steep positive temperature dependencies of Hal(-) ion abundance in the low electron energy region. Molecular NI intensity decreases rapidly with increasing temperature in the case of 1I-AQ. In the case of 2Br-AQ, a metastable NI peak (m/z 22.9) corresponding to the process BrAQ(-) --> Br(-) + AQ(0) was recorded. This means that the characteristic dissociation lifetime of the molecular NI Br-AQ(-) is at least approximately 25 micros at the energy approximately 0.67 eV in the low-temperature spectrum (T approximately 80 degrees C), and at the energy approximately 0.13 eV in the hot spectrum (T approximately 290 degrees C). Together with the observed temperature dependence of the 2Br-AQ curves of effective yield (CEY), this proves that this anion dissociates according to Coulson's model. The same halogen anion behavior is observed in the case of 1Cl-AQ. There are three consecutive stages in the process of molecular NI dissociation of Cl- and Br-substituted AQ, namely, electron capture into the empty pi-orbital by means of the shape resonance mechanism, followed by a radiationless transition into the ground electronic pi-state of the anion, as predicted by Compton in the case of the parabenzoquinone molecule, and, finally, a fluctuative dissociation of the molecular NI accompanied by the transition from the pi-term into the sigma-term, so-called predissociation. Calculations show reasonable agreement with the experimental data. In the case of 1I-AQ, an effect of inversion of empty levels in the process of electron capture by the molecule takes place, a violation of the so-called frozen shell approximation. The phenomenon found may be of significance not only in the case of ECNI-MS, but also in other experimental investigations using low-energy electron-molecule and ion-molecule collisions.