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11.
Non-empirical SCF-MO molecular wavefunctions were computed for the two limiting structures of C2H2F+ with full geometry optimization using double-zeta quality atomic orbital basis sets. The bridged structure (fluorenium ion) was found to be an energy maximum (transition state) about 31 kcal/mole higher than the open structure (fluoro-vinyl cation). The latter, contrary to the unsubstituted vinyl cation, is slightly (4.5 °) bent away from fluorine at the electron deficient centre. 相似文献
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Riccardo Destro Emanuele Ortoleva Giorgio Modena Lucia Pasquato Vittorio Lucchini 《Helvetica chimica acta》2001,84(4):860-866
Four‐membered ring thiosulfonium ions may be obtained quantitatively and under mild conditions by anionotropic rearrangement of C‐(tert‐butyl)‐substituted thiiranium ion precursors. Thus, t‐4‐(tert‐butyl)‐r‐1,2,2,c‐3‐tetramethylthietanium tetrafluoroborate or hexachloroantimonate ( 2a or 2b , resp.) were formed from thiiranium ion 1 . The thietanium salts 2a and 2b were characterized by X‐ray crystal‐structure analysis. Their cation geometry was also optimized by ab initio calculations at the RHF/6‐31G*//RHF/6‐31G* level, as were those of its stereoisomer 3 and of the unsubstituted S‐methylthietanium ion 5 . Comparison of 2 , 3 , and 5 with 4 – the only other thietanium ion studied by XRD, where the C‐atoms of the thioniacyclobutane ring are part of a trinorbornane skeleton – indicates that, in these systems, relief from substituent overcrowding is easily achieved by a folding of the four‐membered ring along the line connecting the two opposite C‐atoms. The corresponding ring‐deformation normal mode has a calculated frequency as low as 109 cm−1 in ion 5 , to be compared with a frequency of 138 cm−1 in methylcyclobutane. For thietanium ion 2 , the frequencies of the two normal modes involving such ring deformation have calculated values of 61 and 85 cm−1. 相似文献
14.
Paola Taddei Enrico Modena Francesco Traina Saverio Affatato 《Journal of Raman spectroscopy : JRS》2012,43(12):1868-1876
Since the introduction of ceramic‐on‐ceramic couplings in total hip arthroplasty, continuous efforts have been performed to improve the performance of the prosthetic components. To expand the applications of ceramics, in 2000 an innovative alumina–zirconia composite was introduced in the market. The present study represents the first investigation aimed at characterising at the molecular level Biolox® delta retrievals implanted between 1999 and 2009. Fluorescence and Raman results showed that a progressive improvement of the material properties has occurred in the period between 1999 and 2009. Raman spectroscopy showed that wear was the main cause of the in vivo tetragonal‐to‐monoclinic zirconia transformation. Our findings validated the in vitro accelerated ageing protocols proposed in the literature to simulate the effects of the in vivo wear, because the mechanism operating in vivo was found to be the same active in vitro. The in vitro fracture of a new femoral head appeared to be an extreme wear condition that determined the most significant changes in the residual stress state and monoclinic content both in the section of the fragments and on their surface. The micro‐Raman mapping of the fractured articulating surface showed that the tetragonal‐to‐monoclinic transformation involved a region much more extended than as reported in the literature. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
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M. G. Castellano M. Bassan P. Carelli E. Coccia C. Cosmelli V. Fafone I. Modena 《Il Nuovo Cimento C》1992,15(2):219-225
Summary We present noise measurements made at temperatures down to 200 mK on a tunnel junction d.c. SQUID, to be used as amplifier
for the gravitational-wave experiment Nautilus of the Rome group. We find that the flux noise decreases with temperature,
as expected, with a best measured value of
at 0.2 K. The presence of an excess noise term independent of temperature is discussed. 相似文献
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Raoult F Boscheron AC Husson D Sauteret C Modena A Malka V Dorchies F Migus A 《Optics letters》1998,23(14):1117-1119
We demonstrate efficient generation of picosecond narrow-bandwidth pulses by frequency mixing of broadband opposite chirped pulses in a type I doubling crystal. This procedure allows us to produce picosecond pulses that are perfectly synchronized with femtosecond pulses. The experiment shows a decrease of the initial bandwidth by a factor of more than 30, while a high conversion efficiency is maintained. 相似文献
20.
P. Astone M. Bassan R. Bizzarri P. Bonifazi L. Brocco P. Carelli E. Coccia C. Cosmelli A. Degasperis S. Frasca V. Fafone E. Majorana I. Modena G. Modestino A. Moleti G.V. Pallottino G. Pizzella P. Puppo P. Rapagnani F. Ricci R. Terenzi M. Visco 《The European Physical Journal C - Particles and Fields》1998,5(4):651-664
We present an experiment performed to study the behaviour of the dynamic gravitational interaction at laboratory scale. We
used as field generator a mass quadrupole rotating in the range of 460 Hz and we detected the acceleration field with the
cryogenic gravitational wave antenna Explorer of the Rome group. We report the measurements of this interaction as a function
of the distance between the field source and the detector. An upper limit on the parameters of a Yukawa-like potential, modeling
an hypotetic deviation from the Newtonian law of gravity, is derived.
Received: 14 June 1998 / Published online: 16 September 1998 相似文献