Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

New results on photoion pair formation from application of the velocity imaging photoionisation coincidence technique

The velocity imaging photoionisation coincidence (VIPCO) technique is shown to be a powerful tool for studies of ion pair formation. Sequential mechanisms are demonstrated for some three-body ion pair formation reactions. Observation of a new type of reaction producing one negatively and two positively charged ions plus an electron is reported.     

Double photoionisation spectra of small molecules and a new empirical rule for double ionisation energies

Complete double photoelectron spectra are presented for 18 small molecules where the location of charges in the cations and dications is relatively clearly defined. The data demonstrate the importance of a coulombic repulsion contribution to the double ionisation energies. Examination of data for a wide range of molecules leads to a new empirical rule to calculate double ionisation energies from the molecules’ single ionisation energies and maximum dimensions. Where single and double ionisation energies are known the rule allows the deduction of plausible intercharge distances.     

Valence double ionization of O2 at photon energies below and above the molecular double ionization threshold

A recently developed time-of-flight photoelectron-photoelectron coincidence spectroscopy technique, which gives complete two-dimensional e(-)-e(-) spectra in single photon double ionization, is applied to molecular oxygen at photon energies below and above the adiabatic double ionization threshold of O(2). Analysis of the two-dimensional coincidence maps reveals specific indirect pathways for the double ionization process. Dissociative ionization paths with subsequent autoionization of atomic oxygen are found to be the dominant processes for all chosen photon energies. Spectra of the photoelectrons coincident with the autoionization electrons show that intermediate O(2)(+) states are involved which do not autoionize to molecular O(2)(2+). In particular, the ground state of O(2)(2+) is vibrationally resolved and shows a regular progression which can be well described by direct Franck-Condon transitions at an internuclear distance R(e)(X (1)Sigma(g)(+))=1.054 A. Quantum yields of double ionization for O(2), of a form discussed in this paper, are determined.     

The predissociations of water ions

Experimental relative abundances of D₂O⁺, OD⁺ and D⁺ ions are given as functions of the initial energy of D₂O⁺ ions in the B?²B₂ state. The D⁺ ions are more abundant than expected on the basis of a recent theoretical model. Less kinetic energy is released in D⁺ formation than in OD⁺ formation, for the same excess energy available. It is suggested that OD⁺ formation should be modelled as a statistical reaction, whereas D⁺ formation is more specific. No detailed model can be suggested on present evidence, but it is pointed out that H₂O⁺ (B?²B₂) can be predissociated to OH⁺ by the X? state to H⁺ by the à state, as well as by repulsive states.     

A theoretical and experimental study of the SO2(2+) dication

The double photoionization spectrum of SO2 has been measured using the TOF-PEPECO technique and contains one resolved band. Detailed electronic structure calculations and experimental comparisons allow the resolved band to be identified as the A 1A2 state of the SO2(2+) dication, with its adiabatic ionization energy at 35.284+/-0.02 eV. According to the most accurate calculations, the ground state level of SO2(2+) must be located near 33.48 eV, well below the range accessed by vertical transitions from neutral SO2. Transient SO2 (2+) molecules detected by mass spectrometry may be identified either as the sharp levels of the A 1A2 state or as ground state levels populated by nonvertical ionization pathways.     

The band 12 issue in the electron momentum spectra of norbornane: a comparison with additional Green's Function calculations and ultraviolet photoemission measurements

In continuation of a recent study of the electronic structure of norbornane [J. Chem. Phys., 2004, 121, 10525] by means of electron momentum spectroscopy (EMS), we present Green's Function calculations of the ionization spectrum of this compound at the ADC(3) level using basis sets of varying quality, along with accurate evaluations at the CCSD(T) level of the vertical (26.5 eV) and adiabatic (22.1 eV) double ionization thresholds under C(2v) symmetry. The obtained results are compared with newly recorded ultraviolet photoemission spectra (UPS), up to binding energies of 40 eV. The theoretical predictions are entirely consistent with experiment and indicate that, in a vertical depiction of ionization, shake-up states at binding energies larger than approximately 26.5 eV tend to decay via emission of a second electron in the continuum. A band of s-type symmetry that has been previously seen at approximately 25 eV in the electron impact ionization spectra of norbornane is entirely missing in the UPS measurements and theoretical ADC(3) spectra. With regard to these results and to the time scales characterizing electron-electron interactions in EMS (10(-17) s) as compared with that (10(-13) s) of photon-electron interactions in UPS, and considering the p-type symmetry of the electron momentum distributions for the nearest 1b(1) and 1b(2) orbitals, this additional band can certainly not be due to adiabatic double ionization processes starting from the ground electronic state of norbornane, or to exceptionally strong vibronic coupling interactions between cationic states derived from ionization of the latter orbitals. It is therefore tentatively ascribed to autoionization processes via electronically excited and possibly dissociating states.     

Photon time-of-flight spectroscopy

The feasibility of photon time-of-flight spectroscopy using optical waveguides is demonstrated     

Observation of a molecular frame (e, 2e) cross section: an (e, 2e + M) triple coincidence study on H(2)

We report the first experimental results showing transition-specific anisotropy of molecular frame (e, 2e) cross sections. Vector correlations between the two outgoing electrons and the fragment ion have been measured for specific ionization-excitation processes of H2. The results enable us to obtain molecular frame (e, 2e) cross sections for transitions to the 2ssigma(g) and 2psigma(u) excited states of H(2)(+), thereby making stereodynamics of the electron-molecule collisions directly visible.