The relationship between the population of the V(N), V(O1) basins and the
N–O1 bond length is shown in Fig. 19.6. The protocovalent bond is observed for
two shortest N–O1 bonds in IONO (syn, 1.348 Å) and BrONO (syn, 1.403 Å). For
much longer N–O1 bonds in the syn forms of FONO and ClONO (r(N,
O1) > 1.48 Å) also for all anti conformers of FONO, ClONO, BrONO and IONO
(r(N,O1) > 1.50 Å), the V(O) nonbonding attractor is no longer observed. Two
types of ELF-topology (II and III), identified for the N–O1 bond are in agreement
with the expected evolution of the V(N,O1) bonding basin in a process of the N–O1
bond dissociation. In such process the V(N,O1) bonding basin is annihilated first
and then two non-bonding basins are observed V(N), V(O1). Further elongation of
the N–O1 bond results in annihilation of V(O1) and subsequently the V(N) basin.
The core and valence attractors localised in three conformers of the peroxynitrous acid molecule are shown in Fig. 19.7. Values of the basin populations can be
found in Table 19.3. Comparison of the N–O1 bond lengths show relatively short
bond for the syn-syn conformer (1.393 Å), which is 0.112 and 0.105 Å shorter than
in the syn-perp and anti-perp conformers. Topological analysis of ELF shows single
valence attractor between the C(N) and C(O1) core attractors for all conformers. In
the syn-perp and anti-perp isomers with longer N–O1 bond, only the V(N) attractor
is observed. The basin populations are 0.46e for both isomers. The same population
value is a result of a very small difference between the N–O1 bond lengths
(0.007 Å). For the syn-syn conformer, a single valence attractor is found in the
vicinity of the O1 atom whereas the single V(N) attractor is observed in the vicinity
of N atom. It is classified as disynaptic bonding attractor, V(N,O1). The basin
population of 0.91e is much larger than the one calculated for the single V(N) basin
Fig. 19.6 The correlation between the population of V(N), V(O1) basins and the r(N–O1) bond
length in the halogen nitrites, XO1NO2
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S. Berski and A.J. Gordon
N–O1 bond length is shown in Fig. 19.6. The protocovalent bond is observed for
two shortest N–O1 bonds in IONO (syn, 1.348 Å) and BrONO (syn, 1.403 Å). For
much longer N–O1 bonds in the syn forms of FONO and ClONO (r(N,
O1) > 1.48 Å) also for all anti conformers of FONO, ClONO, BrONO and IONO
(r(N,O1) > 1.50 Å), the V(O) nonbonding attractor is no longer observed. Two
types of ELF-topology (II and III), identified for the N–O1 bond are in agreement
with the expected evolution of the V(N,O1) bonding basin in a process of the N–O1
bond dissociation. In such process the V(N,O1) bonding basin is annihilated first
and then two non-bonding basins are observed V(N), V(O1). Further elongation of
the N–O1 bond results in annihilation of V(O1) and subsequently the V(N) basin.
The core and valence attractors localised in three conformers of the peroxynitrous acid molecule are shown in Fig. 19.7. Values of the basin populations can be
found in Table 19.3. Comparison of the N–O1 bond lengths show relatively short
bond for the syn-syn conformer (1.393 Å), which is 0.112 and 0.105 Å shorter than
in the syn-perp and anti-perp conformers. Topological analysis of ELF shows single
valence attractor between the C(N) and C(O1) core attractors for all conformers. In
the syn-perp and anti-perp isomers with longer N–O1 bond, only the V(N) attractor
is observed. The basin populations are 0.46e for both isomers. The same population
value is a result of a very small difference between the N–O1 bond lengths
(0.007 Å). For the syn-syn conformer, a single valence attractor is found in the
vicinity of the O1 atom whereas the single V(N) attractor is observed in the vicinity
of N atom. It is classified as disynaptic bonding attractor, V(N,O1). The basin
population of 0.91e is much larger than the one calculated for the single V(N) basin
Fig. 19.6 The correlation between the population of V(N), V(O1) basins and the r(N–O1) bond
length in the halogen nitrites, XO1NO2
540
S. Berski and A.J. Gordon