The loss of a methyl radical and the retro diels—Alder reaction in the electron impact mass spectrometry of 2-cyclohexen-1-ol and related compounds

The electron impact mass spectra of 2-cyclohexen-1-ol and of several of its ²H and ¹³C labelled analogues show that the molecular ions lose a methyl radical by a completely different means from the mechanism described previously. Moreover, the retro Diels–Alder reaction also proceeds in a non-classical way; in addition to the elimination of an olefinic molecule from unrearranged molecular ions, a second more important route implies a formal 1,3 allylic rearrangement prior to the retro Diels–Alder reaction. The mass spectra of a series of alkyl substituted homologues show that the competition between the two processes is closely related to the size of the olefinic moiety that is expelled.     

Electron impact mass spectrometry of 3-cyclohexen-1-ol and related compounds

The electron impact mass spectrum of 3-cyclohexen-1-ol has been studied, especially with regard to the retro Diels-Alder reaction. Six deuterium labelled analogues and two dimethyl substituted homologues were synthesized. Contrary to what we have observed with 2-cyclohexen-1-ol, the double bond migration which precedes the retro Diels-Alder reaction plays a minor role.     

On the a.s. Cesàro-α convergence for stationary or orthogonal random variables

We give a new direct proof of the a.s. convergence of the Cesàro- means of a stationary process (X _n) when 0<<1 andE(X _n ^p )<+ with p>1 and we show that this result does not hold in general for p=1. We also consider similar questions for orthogonal random variables. Finally, we study the a.s. convergence of Riesz harmonic means.     

C2GT: intercepting CERN neutrinos to Gran Sasso in the Gulf of Taranto to measure θ13

Today’s greatest challenge in accelerator-based neutrino physics is to measure the mixing angle θ₁₃ which is known to be much smaller than the solar mixing angle θ₁₂ and the atmospheric mixing angle θ₂₃. A non-zero value of the angle θ₁₃ is a prerequisite for observing CP violation in neutrino mixing. In this paper, we discuss a deep-sea neutrino experiment with 1.5 Mt fiducial target mass in the Gulf of Taranto with the prime objective of measuring θ₁₃. The detector is exposed to the CERN neutrino beam to Gran Sasso in off-axis geometry. Monochromatic muon neutrinos of ≈ 800 MeV energy are the dominant beam component. Neutrinos are detected through quasi-elastic, charged-current reactions in sea water; electrons and muons are detected in a large-surface, ring-imaging Cherenkov detector. The profile of the seabed in the Gulf of Taranto allows for a moveable experiment at variable distances from CERN, starting at 1100 km. From the oscillatory pattern of the disappearance of muon neutrinos, the experiment will measure sin²θ₂₃ and especially Δm² ₂₃ with high precision. The appearance of electron neutrinos will be observed with a sensitivity to P(ν_μ→ν_e) as small as 0.0035 (90% CL) and sin²θ₁₃ as small as 0.0019 (90% CL; for a CP phase angle δ=0° and for normal neutrino mass hierarchy).     

Ultrafast excited-state dynamics of rhenium(I) photosensitizers [Re(Cl)(CO)3(N,N)] and [Re(imidazole)(CO)3(N,N)]+: diimine effects

Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L = Cl, n = 0; L = imidazole, n = 1+) were investigated using fluorescence up-conversion, transient absorption in the 650-285 nm range (using broad-band UV probe pulses around 300 nm) and picosecond time-resolved IR (TRIR) spectroscopy in the region of CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing to at least two hot triplet states with a rate that is faster in Cl (～100 fs)(-1) than in imidazole (～150 fs)(-1) complexes but essentially independent of the N,N ligand. TRIR spectra indicate the presence of two long-lived triplet states that are populated simultaneously and equilibrate in a few picoseconds. The minor state accounts for less than 20% of the relaxed excited population. UV-vis transient spectra were assigned using open-shell time-dependent density functional theory calculations on the lowest triplet CT state. Visible excited-state absorption originates mostly from mixed L;N,N(?-) → Re(II) ligand-to-metal CT transitions. Excited bpy complexes show the characteristic sharp near-UV band (Cl, 373 nm; imH, 365 nm) due to two predominantly ππ*(bpy(?-)) transitions. For phen and dmp, the UV excited-state absorption occurs at ～305 nm, originating from a series of mixed ππ* and Re → CO;N,N(?-) MLCT transitions. UV-vis transient absorption features exhibit small intensity- and band-shape changes occurring with several lifetimes in the 1-5 ps range, while TRIR bands show small intensity changes (≤5 ps) and shifts (～1 and 6-10 ps) to higher wavenumbers. These spectral changes are attributable to convoluted electronic and vibrational relaxation steps and equilibration between the two lowest triplets. Still slower changes (≥15 ps), manifested mostly by the excited-state UV band, probably involve local-solvent restructuring. Implications of the observed excited-state behavior for the development and use of Re-based sensitizers and probes are discussed.