Angular correlation of electrons in the ground state of helium

The spatial angular correlation of electrons in the ground state of the helium atom has been examined using configuration interaction and Hylleraas wave-functions. It was found that, in general, the average angle between the electrons is not a maximum when the two electrons are at the same distance from the nucleus. For configuration interaction wave-functions there is a position of the electrons for which the average value of the angle between the electrons is a maximum. Hylleraas wave-functions do not show this behavior.     

Electron-photon polarisation correlations in 140 eV electron impact excitation of helium

Electron-polarised photon coincidence techniques are used to determine linear and circular polarisation correlations from the differential electron impact excitation of the 2¹ P state of helium at an incident electron energy of 140 eV. At 30° and 45° electron scattering angles, all the Stokes parameters are determined, whereas at 52.5° onlyP ₂ is measured. Comparisons are made with the distorted wave (DW) calculations of Madison [11] and the first order many-body theory (FOMBT) of Cartwright and Csanak [4].     

Electron spectroscopy study of the 27.5 eV satellite line in acetylene excited by synchrotron radiation

Valence electron spectra from acetylene using synchrotron radiation with 50 and 70 eV excitation energy are presented. The 27.5 eV satellite line is resolved into two components. The intensities of these satellite lines are compared to the previously measured intensities at 1487 eV excitation energy. β values for the satellite lines and for all the valence levels are determined at 70 eV excitation enery. A previously unknown satellite line is found at 31.0 eV binding energy. This line corresponds to an onset of the double ionization continuum.     

A correlation of excited state rotational constants for diatomic molecules

The concepts of “orbital stress” and “transition stress” are defined and applied to N₂, N⁺₂, CO, and CO⁺. The bond lengths and rotational constants of excited electronic states are related to the transition stress, and the response of the electrons and nuclei to the transition stress is shown to be a molecular property, essentially independent of the electronic configuration or state.     

Angular momentum coherences of helium atoms excited by proton impact

Using electric-field anticrossing techniques, we investigated the coherent excitation ofn=5–8 He I states with different orbital angular momenta by proton impact. These measurements give strong evidence that saddle dynamics of H ₂ ⁺ -like systems are well suited for describing the final phase of 12.5 keV H⁺-He collisions. We conclude that, besides electron promotion via the 2pσ orbital, the collision system undergoes diabatic 1sσ–3dσ transitions during the close encounter and present an explanation of the electric dipole moments measured for excitation of H(n=2) states by H⁺-He and H-He collisions.     

A correlation study of Li ground state by the MCHF procedure

Results are reported for multiconfiguration Hartree–Fock studies of correlation in the lithium ground state, which maintain orthogonality of orbitals within a configuration. It is shown that when the 1s- and 2s-orbitals are fixed at their Hartree–Fock value, configurations for which Brillouin's theorem holds may be important, particularly for atomic properties other than energy. The Fermi contact term is considered as an example.     

On the importance of excited state dynamic response electron correlation in polarizable embedding methods

We investigate the effect of including a dynamic reaction field at the lowest possible ab inito wave function level of theory, namely the Hartree‐Fock (HF) self‐consistent field level within the polarizable embedding (PE) formalism. We formulate HF based PE within the linear response theory picture leading to the PE–random‐phase approximation (PE–RPA) and bridge the expressions to a second‐order polarization propagator approximation (SOPPA) frame such that dynamic reaction field contributions are included at the RPA level in addition to the static response described at the SOPPA level but with HF induced dipole moments. We conduct calculations on para‐nitro‐aniline and para‐nitro‐phenolate using said model in addition to dynamic PE–RPA and PE–CAM–B3LYP. We compare the results to recently published PE–CCSD data and demonstrate how the cost effective SOPPA‐based model successfully recovers a great portion of the inherent PE–RPA error when the observable is the solvatochromic shift. We furthermore demonstrate that whenever the change in density resulting from the ground state‐excited state electronic transition in the solute is not associated with a significant change in the electric field, dynamic response contributions formulated at the HF level of theory manage to capture the majority of the system response originating from derivative densities. © 2012 Wiley Periodicals, Inc.     

Approximate symmetries in the singly excited states of helium

Consideration of R(4) as the degeneracy group for the singly excited states of helium allows the assignment of R(4) irreducible representations (irreps) to these states. Induction of these irreps onto the irreps of SU(4) and U(4) provides a sufficient number of invariants to define the energy levels. Empirical equations allow all of the singlet states to be related to the first ionization energy and the Rydberg constant, to a good approximation. Empirical equations can also be derived for the triplet states, but their relation to the ionization energy and/or the Rydberg constant is not obvious.     

Estimation of the ground state correlation energy for isoelectronic series of 2 to 20 electrons

Correlation energies for all isoelectronic sequences of 2 to 20 electrons andZ=2 to 25 are obtained by taking differences between theoretical total energies of Dirac-Fock calculations and experimental total energies. These are pure relativistic correlation energies because relativistic and QED effects are already taken care of. The theoretical as well as the experimental values are analysed critically in order to get values as accurate as possible. The correlation energies obtained show an essentially consistent behaviour fromZ=2 to 17. ForZ>17 inconsistencies occur indicating errors in the experimental values which become very large forZ>25.     

Post collision interaction effects in the ionisation of helium and hydrogen by fast electrons

Conspicuous effects from a weak post collision interaction have been identified in triply differential cross sections for the ionisation of helium and hydrogen by fast electrons. A classical correction to a first Born approximation describes experimental data at smaller values of the momentum transfer.     

Computational study of thioflavin T torsional relaxation in the excited state

Quantum-chemical calculations of the Thioflavin T (ThT) molecule in the ground S0 and first excited singlet S1 states were carried out. It has been established that ThT in the ground state has a noticeable nonplanar conformation: the torsion angle phi between the benzthiazole and the dimethylaminobenzene rings has been found to be approximately 37 degrees. The energy barriers of the intramolecular rotation appearing at phi = 0 and 90 degrees are quite low: semiempirical AM1 and PM3 methods predict values approximately 700 cm-1 and ab initio methods approximately 1000-2000 cm(-1). The INDO/S calculations of vertical transitions to the S1(abs) excited state have revealed that energy ES1(abs) is minimal for the twisted conformation with phi = 90 degrees and that the intramolecular charge-transfer takes place upon the ThT fragments' rotation from phi = 0 to 90 degrees. Ab initio CIS/RHF calculations were performed to find optimal geometries in the excited S1 state for a series of conformers having fixed phi values. The CIS calculations have predicted a minimum of the S1 state energy at phi approximately 21 degrees; however, the energy values are 1.5 times overestimated in comparison to experimental data. Excited state energy dependence on the torsion angle phi, obtained by the INDO/S method, reveals that ES1(fluor) is minimal at phi = approximately 80-100 degrees, and a plateau is clearly observed for torsion angles ranging from 20 to 50 degrees. On the basis of the calculation results, the following scheme of photophysical processes in the excited S1 state of the ThT is suggested. According to the model, a twisted internal charge-transfer (TICT) process takes place for the ThT molecule in the excited singlet state, resulting in a transition from the fluorescent locally excited (LE) state to the nonfluorescent TICT state, accompanied by torsion angle phi growth from 37 to 90 degrees. The TICT process effectively competes with radiative transition from the LE state and is responsible for significant quenching of the ThT fluorescence in low-viscosity solvents. For viscous solvents or when the ThT molecule is located in a rather rigid microenvironment, for example, when it is bound to amyloid fibrils, internal rotation in the dye molecule is blocked due to steric hindrance, which results in suppression of the LE --> TICT quenching process and in a high quantum yield of fluorescence.     

Influence of organic ions on DNA damage induced by 1 eV to 60 keV electrons

We report the results of a study on the influence of organic salts on the induction of single strand breaks (SSBs) and double strand breaks (DSBs) in DNA by electrons of 1 eV to 60 keV. Plasmid DNA films are prepared with two different concentrations of organic salts, by varying the amount of the TE buffer (Tris-HCl and EDTA) in the films with ratio of 1:1 and 6:1 Tris ions to DNA nucleotide. The films are bombarded with electrons of 1, 10, 100, and 60?000 eV under vacuum. The damage to the 3197 base-pair plasmid is analyzed ex vacuo by agarose gel electrophoresis. The highest yields are reached at 100 eV and the lowest ones at 60 keV. The ratios of SSB to DSB are surprisingly low at 10 eV (～4.3) at both salt concentrations, and comparable to the ratios measured with 100 eV electrons. At all characteristic electron energies, the yields of SSB and DSB are found to be higher for the DNA having the lowest salt concentration. However, the organic salts are more efficient at protecting DNA against the damage induced by 1 and 10 eV electrons. DNA damage and protection by organic ions are discussed in terms of mechanisms operative at each electron energy. It is suggested that these ions create additional electric fields within the groove of DNA, which modify the resonance parameter of 1 and 10 eV electrons, namely, by reducing the electron capture cross-section of basic DNA units and the lifetime of corresponding transient anions. An interstrand electron transfer mechanism is proposed to explain the low ratios for the yields of SSB to those of DSB produced by 10 eV electrons.     

Solvation and thermalization of electrons generated by above-the-gap (12.4 eV) two-photon ionization of liquid H2O and D2O

Temporal evolution of transient absorption (TA) spectra of electrons generated by above-the-gap (12.4 eV total energy) two-photon ionization of liquid H2O and D2O has been studied on femto- and picosecond time scales. The spectra were obtained at intervals of 50 nm between 0.5 and 1.7 mum. Two distinct regimes of the spectral evolution were observed: t < 1 ps and t > 1 ps. In both of these regimes, the spectral profile changes considerably with the delay time of the probe pulse. The "continuous blue shift" and the "temperature jump" models, in which the spectral profile does not change as it progressively shifts, as a whole, to the blue, are not supported by our data. Furthermore, no p-state electron, postulated by several authors to be a short-lived intermediate of the photoionization process, was observed by the end of the 300 fs, 200 nm pump pulse. For t < 1 ps, two new TA features (the 1.15 microm peak and 1.4 mum shoulder) were observed for the electron in the spectral region where O-H overtones appear in the spectra of light water. These two features were not observed for the electron in D2O. The 1.4 mum peak observed in D2O may be the isotope-shift analogue of the 1.15 microm feature in H2O. Vibronic coupling to the modes of water molecules lining the solvation cavity is a possible origin of these features. On the sub-picosecond time scale, the absorption band of solvated electron progressively shifts to the blue. At later delay times (t > 1 ps), the position of the band maximum is "locked", but the spectral profile continues to change by narrowing on the red side and broadening on the blue side; the oscillator strength is constant within 10%. The time constant of this narrowing is ca. 0.56 ps for H2O and 0.64 ps for D2O. Vibrational relaxation and time-dependent decrease in the size and sphericity of the solvation cavity are suggested as possible causes for the observed spectral transformations in both of these regimes.     

Dehydrogenation of adenine induced by slow (<3 eV) electrons

Low energy (<3 eV) electrons impact to gas phase Adenine generates the dehydrogenated Adenine negative fragments, (A–H)⁻, and an H-atom neutral radical counterpart. Within the energy range of 0.7–2.8 eV, production of (A–H)⁻ arises from Dissociative Electron Attachment (DEA). In addition, a sharp peak is observed at near 0 eV. This peak is identified to arise from dissociative electron transfer reaction of SF₆⁻ (from the calibration gas) with Adenine.