According to [113, 116], the n X = 0, 1 and 2 vdW modes are located in the
collinear (He
… I−Cl), T-shaped and antilinear (He
… Cl−I) wells, respectively
(Fig. 6.34).
Their energies relative to the HeI
35 Cl(X, v X = 0) dissociation limit are equal to
−18.29, −15.14 and −11.76, units, cm
−1 , respectively. The three energy minima are
separated by the isomerization barriers: h = 0 and T-shaped wells, with the energy
of −15.3 cm
−1 (*42.9 cm
−1 above the collinear well), whereas the T-shaped and
antilinear wells by the barrier with energy of −2.8 cm
−1 (*35.4 cm
−1 above the
collinear well) [113].
The locations of the n B vdW modes are shown in (d)-(h) panels in Fig. 6.34. The
n B = 0 lowest energy vdW level is bound by 13.30 cm
−1 and is localized in the near
T-shaped well. The next higher n B = 1 level has a node in the angular coordinate,
but is still localized in the T-shaped well. The n B = 2, 3 and 4 levels, at −6.21,
−5.09 and −3.63, units, cm
−1 , have angular nodes, become delocalized in the
angular coordinate and thus are free-rotor levels [116].
The excitation spectrum of the HeICl(B,3) VP product luminescence, experimental and calculated action spectra of the HeI
35 Cl(E,11) VP products [116] are
given in Fig. 6.35.
The assignments of the action spectra bands are correct, though calculated and
observed transition energies do not coincide. Besides, the T-shaped HeI
35 Cl(B,3,
n B = 1 ← X,0,n X = 1) transition has not been observed in the experiment.
Excitation spectra of the luminescence of the HeI
35 Cl(E,11, b,1) VP and EP
products are given in Fig. 6.36.
Fig. 6.34 Plots of the J = 0 He
…
I
35
Cl probability amplitudes for the n X = 0-2 vdW modes of the
the HeI
35
Cl(X,v X = 0) state, (a)-(c) panels, respectively, and the n B = 0-4 vdW modes the HeI
35
Cl
(B,v B = 3) state, (d)-(h) panels, respectively (see [116]) (Reproduced from A.B. McCoy, J.P. Darr,
D.S. Boucher, P.R. Winter, M.D. Bradke, R.A. Loomis, J. Chem. Phys. 120, 2677-2685 (2004).
https://doi.org/10.1063/1.1636693 with the permission of AIP Publishing)
6.3 Van der Waals Complexes
243
collinear (He
… I−Cl), T-shaped and antilinear (He
… Cl−I) wells, respectively
(Fig. 6.34).
Their energies relative to the HeI
35 Cl(X, v X = 0) dissociation limit are equal to
−18.29, −15.14 and −11.76, units, cm
−1 , respectively. The three energy minima are
separated by the isomerization barriers: h = 0 and T-shaped wells, with the energy
of −15.3 cm
−1 (*42.9 cm
−1 above the collinear well), whereas the T-shaped and
antilinear wells by the barrier with energy of −2.8 cm
−1 (*35.4 cm
−1 above the
collinear well) [113].
The locations of the n B vdW modes are shown in (d)-(h) panels in Fig. 6.34. The
n B = 0 lowest energy vdW level is bound by 13.30 cm
−1 and is localized in the near
T-shaped well. The next higher n B = 1 level has a node in the angular coordinate,
but is still localized in the T-shaped well. The n B = 2, 3 and 4 levels, at −6.21,
−5.09 and −3.63, units, cm
−1 , have angular nodes, become delocalized in the
angular coordinate and thus are free-rotor levels [116].
The excitation spectrum of the HeICl(B,3) VP product luminescence, experimental and calculated action spectra of the HeI
35 Cl(E,11) VP products [116] are
given in Fig. 6.35.
The assignments of the action spectra bands are correct, though calculated and
observed transition energies do not coincide. Besides, the T-shaped HeI
35 Cl(B,3,
n B = 1 ← X,0,n X = 1) transition has not been observed in the experiment.
Excitation spectra of the luminescence of the HeI
35 Cl(E,11, b,1) VP and EP
products are given in Fig. 6.36.
Fig. 6.34 Plots of the J = 0 He
…
I
35
Cl probability amplitudes for the n X = 0-2 vdW modes of the
the HeI
35
Cl(X,v X = 0) state, (a)-(c) panels, respectively, and the n B = 0-4 vdW modes the HeI
35
Cl
(B,v B = 3) state, (d)-(h) panels, respectively (see [116]) (Reproduced from A.B. McCoy, J.P. Darr,
D.S. Boucher, P.R. Winter, M.D. Bradke, R.A. Loomis, J. Chem. Phys. 120, 2677-2685 (2004).
https://doi.org/10.1063/1.1636693 with the permission of AIP Publishing)
6.3 Van der Waals Complexes
243