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spectrometer works at constant analyzer energy and is monitored
References and notes
by a microcomputer supplemented by a digital–analogue converter.
The spectra resulting from a single scan are built from 2048 points
and are accurate within 0.05 eV. They are calibrated against the
autoionization of xenon at 12.13 and 13.45 eV, and nitrogen at 15.59
and 16.98 eV. Compound 1b was slowly vaporized at low pressure
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internal, progressively heated, FVT quartz furnace (furnace length
20 cm) built into the PE spectrometer. The in situ generated com-
pounds were then directly conducted to the ionization chamber
(the distance between the oven exit and the ionization head does
not exceed 5 cm) and analyzed.
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energies were calculated with
D
SCFꢂDFT, which means that sep-
arate SCF calculations were performed to optimize the orbitals of
the ground state and the appropriate excited state determinants
(IE¼EcationꢂEneut.mol.). TDDFT21 approach provides a first principle
method for the calculation of excitation energies within a density
functional context taking into account the low lying ion calculated
by DSCF method. The vertical ionization energies of the compounds
1–4 were also calculated at the ab initio level according to OVGF23
method. In this case the effects of electron correlation and re-
organization are included beyond the Hartree–Fock approximation,
and the self-energy part was expanded up to third order. To com-
pare the ionization energies resulting from these rigorous methods
of calculation, we also used a current estimation of ionization en-
ergies. Indeed, it has been shown31 that 3Ki S could be correlated with
experimental vertical ionization energies (IEv) by a uniform shift
x¼jꢂ3i (HOMO)ꢂIEevxpj. This approach gives a remarkable agree-
ment with experimental values and is justified by the fact that the
first calculated vertical ionization potential lies very close to
experimental values. Stowasser and Hoffman32 have shown that
the localizations of KS orbitals are very similar to those obtained
after HF calculations. The advantages of the most employed method
of calculations of the first ionization energies (
DSCFꢂDFT calcula-
tions) have been thoroughly demonstrated.24,33
Acknowledgements
30. (a) Parr, R. G.; Yang, W. Functional Theory of Atoms and Molecules; Oxford
University Press: New York, NY, 1989; (b) Frish, M. J.; Trucks, G. W.; Cheeseman,
J. R. Systematic Model Chemistries Based on Density Functional Theory:
Comparison with Traditional Models and with Experiment. In Recent
Development and Applications of Modern Density Functional Theory, Theoretical
and Computational Chemistry; Semminario, J. M., Ed.; Elsevier Science B.V:
Amsterdam–Lausanne–New York–Oxford–Shannon–Tokyo, 1996; Vol. 4,
pp 679–707.
´
´
The authors thank the Rector of the University of qodz for fi-
`
nancial support (Grant 505/740). The authors thank P. Baylere for
his efficient technical assistance.
Supplementary data
31. (a) Arduengo, A. J.; Bock, H.; Chen, H.; Denk, M.; Dixon, D. A.; Green, J. C.; Her-
mann, W. A.; Jones, N. L.; Wagner, M.; West, R. J. Am. Chem. Soc. 1994, 116, 6641–
6649; (b) Muchall, H.; Werstiuk, N.; Pitters, J.; Workentin, M. Tetrahedron 1999,
55, 3767–3778; (c) Muchall, H.; Werstiuk, N.; Choudury, B.; Ma, J.; Warkentin, J.;
Pezacki, J. Can. J. Chem. 1998, 76, 238–240; (d) Muchall, H.; Werstiuk, N.;
Choudury, B. Can. J. Chem. 1998, 76, 221–227; (e) Muchall, H.; Rademacher, P.
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Calculated and experimental values of ionization energies for
N-allyl-2-cyano-3-phenylazetidine (1a), calculated geometrical
parameters for the isomers of N-allyliminoacetonitrile (2b), and the
rotamers of N-cyanomethyl-1-aza-1,3-butadiene (3b), calculated
total energies of iminoacetonitrile 2b and the rotamers of azabu-
tadiene 3b, calculated (E)- and (Z)-iminonitrile 2b isomerization
pathways to s-cis and s-trans N-cyanomethyl-1-aza-1,3-butadiene
(3a). Supplementary data associated with this article can be found
32. Stowasser, R.; Hoffmann, R. J. Am. Chem. Soc. 1999, 121, 3414–3420.
´
33. (a) Joanteguy, S.; Pfister-Guillouzo, G.; Chermette, H. J. Phys. Chem. 1999,
103, 3505–3511; (b) Chrostowska, A.; Miqueu, K.; Pfister-Guillouzo, G.;
Briard, E.; Levillain, J.; Ripoll, J.-L. J. Mol. Spectrosc. 2001, 205, 323–330;
`
(c) Bartnik, R.; Baylere, P.; Chrostowska, A.; Galindo, A.; Lesniak, S.;
Pfister-Guillouzo, G. Eur. J. Org. Chem. 2003, 2475–2479.