TY - JOUR
T1 - Electronic structure of haloalkanes
T2 - a high resolution photoelectron spectroscopic study
AU - Novak, I.
AU - Klasinc, L.
AU - Kovač, B.
AU - McGlynn, S. P.
PY - 1993/8/13
Y1 - 1993/8/13
N2 - High resolution He(I) photoelectron spectra (PES) of a number of bromo- and iodoalkanes have been measured. Linear relationships between ionization energies (Ei) and 1/n (where n is the number of carbon atoms in the chain) describe the trends reasonably well if n = 1 is excluded for dihaloalkanes. This property (i.e. line slopes) when joined the alternation of halogen lone pair bandwidths within a given spin-orbit doublet, can be used to provide a fully empirical assignment of the four non-bonding orbital ionizations of dihaloalkanes. The interactions between the halogen lone pair orbitals and the alkane σ orbitals dominate in dihaloalkanes for which n≥2, while through-space interaction is important only in dihalomethanes (n = 1). Vibrational fine structures were used to infer the existence of hyperconjugative effects.
AB - High resolution He(I) photoelectron spectra (PES) of a number of bromo- and iodoalkanes have been measured. Linear relationships between ionization energies (Ei) and 1/n (where n is the number of carbon atoms in the chain) describe the trends reasonably well if n = 1 is excluded for dihaloalkanes. This property (i.e. line slopes) when joined the alternation of halogen lone pair bandwidths within a given spin-orbit doublet, can be used to provide a fully empirical assignment of the four non-bonding orbital ionizations of dihaloalkanes. The interactions between the halogen lone pair orbitals and the alkane σ orbitals dominate in dihaloalkanes for which n≥2, while through-space interaction is important only in dihalomethanes (n = 1). Vibrational fine structures were used to infer the existence of hyperconjugative effects.
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U2 - 10.1016/0022-2860(93)80193-Y
DO - 10.1016/0022-2860(93)80193-Y
M3 - Article
AN - SCOPUS:0001483695
VL - 297
SP - 383
EP - 391
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
SN - 0022-2860
IS - C
ER -