The spectroscopic characteristics and dynamics of He
35 Cl 2 B0
þ
u
À
Á
VP are
studied relatively good. It has been shown that the binding energies of the lowest
vdW modes of the He
35 Cl 2 (B,v B = 7-12) complexes are * 3.7 cm
−1 less than that
of He
35 Cl 2 (X, v X = 0) one, i.e., equal to (12.83–3.7) % 9.1 cm
−1 (see above). The
He
35 Cl 2 (B,v B ← X, v X = 0) transitions occur in the T-shaped configuration,
R B = (3.9 ± 0.4) Å, and He
35 Cl 2 (B, v B = 8–24) lifetime is 506 ps (v B = 8)– 52.37 ps
(v B = 12) [53], 5.4 ps (v B = 20), 2.5 ps (v B = 24) [54]. The He
35 Cl 2 (B, v B = 8) binding
energies of the n
b = 0–4 vdW levels are (9.39−1.31) cm
−1
. There are no bound
levels in which the vdW stretch is excited for the B states. The He
35 Cl 2 (B,
v B ) ! He + Cl 2 (B, v B −1) VP channel dominates, and bimodal rotational distributions of the Cl 2 (B, v B −1, J B ) VP products takes place [54] (see [57] and references, also). The HeCl 2 (B, v B ) binding energy is small, and Dv B = 1 VP channel is
energetically possible even at v B = 20. The rotational distributions of the Cl 2 (B, v B )
VP shows that Dv B = 2, 3 VP channel should occur even at v B = 12. The signals
due to VP become unobservable above He
35 Cl 2 (B, v B > 24) [54].
The NeCl 2 Complexes. Experimental and calculated data on spectroscopic
characteristics of the NeCl 2 (X) are given in [23, 25, 55, 56, 58–61]. According to
experimental data, the T-shaped NeCl 2 (X, v X = 0) binding energy is D 0 = (60 ± 2)
cm
−1 [59], and R 0 = 3.57(4) Å see [60] and references). Calculations show [55, 56,
58] that linear NeCl 2 (X,0) conformer is also exist, its binding energy is *10 cm
−1
less and equilibrium distances is *0.8 Å larger (Table 6.2), see [56, 58], also. The
NeCl 2 (X, v X = 1, 2) vdW complexes (lifetime, s ! 10
−5 s) were observed in [61].
The Ne
35 Cl 2 (B, v B ← X, v X = 0) transitions occur in the T-shaped configuration
[60]. It has been shown that the binding energies of the lowest vdW modes of the
Ne
35 Cl 2 (B, v B = 6–13) complexes are *6 cm
−1 less than that of Ne
35 Cl 2 (X, v X = 0)
one [60, 61]. It is equal to D 0 = (55 ± 2) cm
−1 (v B = 16, 17, exp.) and (54.4–51.0)
cm
−1 (v B = 11–21, theor.) [25]. The R 0 value is R 0 = 3.52(5) Å for v B = 7– 12 (see
[60] and references). The Ne
35 Cl 2 (B, v B ) lifetimes are (258 ± 42) ps (v B = 9) Ä
(33 ± 2) ps (v B = 13), 11 ps (v B = 16) [60, 61], (11 ± 2 and 6 ± 1) ps (v B = 16 and
Table 6.2 Equilibrium distances R e ( ^ ˚
A), dissociation, D e , and binding, D 0
(1)
, energies (units,
cm
−1
) and vdW stretching ðx
s
e Þ and bending ðx
b
e Þ wavenumbers of the RgCl 2 (X, v X = 0) linear
(H = 0
°
) and T-shaped (H = 90
°
) complexes calculated in the aug-cc-pVTZ1(3s3p2d1f1g) basis
set, r Cl-Cl = 1.988 ^
A [55] (see Fig. 6.1)
RgCl 2 (X)
H
R e
D e
D
a
0
x
str
e
x
b
e
HeCl 2
0
4.17
45.6
0.1
53.2
18.9
90
3.40
43.5
5.8
46.9
28.5
NeCl 2
0
4.21
87.3
49.9
35.6
16.0
90
3.45
88.0
59.1
33.0
24.7
ArCl 2
0
4.45
223.7
178.5
41.5
24.4
90
3.68
215.4
179.6
38.0
33.6
(1)—D 0 ¼ D e À
1
2 x
str
e þ 2x
b
e
À
Á
H ¼ 0
À
Á
, and D 0 ¼ D e À
1
2 x
str
e þ x
b
e
À
Á
H ¼ 90
À
Á
206
6 Weakly-Bound Complexes and Clusters
35 Cl 2 B0
þ
u
À
Á
VP are
studied relatively good. It has been shown that the binding energies of the lowest
vdW modes of the He
35 Cl 2 (B,v B = 7-12) complexes are * 3.7 cm
−1 less than that
of He
35 Cl 2 (X, v X = 0) one, i.e., equal to (12.83–3.7) % 9.1 cm
−1 (see above). The
He
35 Cl 2 (B,v B ← X, v X = 0) transitions occur in the T-shaped configuration,
R B = (3.9 ± 0.4) Å, and He
35 Cl 2 (B, v B = 8–24) lifetime is 506 ps (v B = 8)– 52.37 ps
(v B = 12) [53], 5.4 ps (v B = 20), 2.5 ps (v B = 24) [54]. The He
35 Cl 2 (B, v B = 8) binding
energies of the n
b = 0–4 vdW levels are (9.39−1.31) cm
−1
. There are no bound
levels in which the vdW stretch is excited for the B states. The He
35 Cl 2 (B,
v B ) ! He + Cl 2 (B, v B −1) VP channel dominates, and bimodal rotational distributions of the Cl 2 (B, v B −1, J B ) VP products takes place [54] (see [57] and references, also). The HeCl 2 (B, v B ) binding energy is small, and Dv B = 1 VP channel is
energetically possible even at v B = 20. The rotational distributions of the Cl 2 (B, v B )
VP shows that Dv B = 2, 3 VP channel should occur even at v B = 12. The signals
due to VP become unobservable above He
35 Cl 2 (B, v B > 24) [54].
The NeCl 2 Complexes. Experimental and calculated data on spectroscopic
characteristics of the NeCl 2 (X) are given in [23, 25, 55, 56, 58–61]. According to
experimental data, the T-shaped NeCl 2 (X, v X = 0) binding energy is D 0 = (60 ± 2)
cm
−1 [59], and R 0 = 3.57(4) Å see [60] and references). Calculations show [55, 56,
58] that linear NeCl 2 (X,0) conformer is also exist, its binding energy is *10 cm
−1
less and equilibrium distances is *0.8 Å larger (Table 6.2), see [56, 58], also. The
NeCl 2 (X, v X = 1, 2) vdW complexes (lifetime, s ! 10
−5 s) were observed in [61].
The Ne
35 Cl 2 (B, v B ← X, v X = 0) transitions occur in the T-shaped configuration
[60]. It has been shown that the binding energies of the lowest vdW modes of the
Ne
35 Cl 2 (B, v B = 6–13) complexes are *6 cm
−1 less than that of Ne
35 Cl 2 (X, v X = 0)
one [60, 61]. It is equal to D 0 = (55 ± 2) cm
−1 (v B = 16, 17, exp.) and (54.4–51.0)
cm
−1 (v B = 11–21, theor.) [25]. The R 0 value is R 0 = 3.52(5) Å for v B = 7– 12 (see
[60] and references). The Ne
35 Cl 2 (B, v B ) lifetimes are (258 ± 42) ps (v B = 9) Ä
(33 ± 2) ps (v B = 13), 11 ps (v B = 16) [60, 61], (11 ± 2 and 6 ± 1) ps (v B = 16 and
Table 6.2 Equilibrium distances R e ( ^ ˚
A), dissociation, D e , and binding, D 0
(1)
, energies (units,
cm
−1
) and vdW stretching ðx
s
e Þ and bending ðx
b
e Þ wavenumbers of the RgCl 2 (X, v X = 0) linear
(H = 0
°
) and T-shaped (H = 90
°
) complexes calculated in the aug-cc-pVTZ1(3s3p2d1f1g) basis
set, r Cl-Cl = 1.988 ^
A [55] (see Fig. 6.1)
RgCl 2 (X)
H
R e
D e
D
a
0
x
str
e
x
b
e
HeCl 2
0
4.17
45.6
0.1
53.2
18.9
90
3.40
43.5
5.8
46.9
28.5
NeCl 2
0
4.21
87.3
49.9
35.6
16.0
90
3.45
88.0
59.1
33.0
24.7
ArCl 2
0
4.45
223.7
178.5
41.5
24.4
90
3.68
215.4
179.6
38.0
33.6
(1)—D 0 ¼ D e À
1
2 x
str
e þ 2x
b
e
À
Á
H ¼ 0
À
Á
, and D 0 ¼ D e À
1
2 x
str
e þ x
b
e
À
Á
H ¼ 90
À
Á
206
6 Weakly-Bound Complexes and Clusters