Experimental interrogation of the multidimensional He + ICl(E, v(dagger)) and He + ICl(beta, v(dagger))
Joshua P Darr1, Richard A Loomis
1Department of Chemistry, Washington University, One Brookings Dr., CB 1134 Saint Louis, Missouri 63130, USA.
Abstract:
Resonant two-photon excitation of the T-shaped and linear He...I(35)Cl(X,v(") = 0) complexes is used to access the intermolecular vibrational levels bound within the He + ICl(beta,v(dagger) = 0-2) and He + ICl(E,v(dagger) = 11,12) intermolecular potentials. The excitation utilizes different metastable intermolecular vibrational levels within the He + ICl(A,v(') = 15) and He + ICl(B,v(') = 2,3) potentials to access levels with varying intermolecular vibrational excitation in the ion-pair states. In addition to providing data revealing properties of the He + ICl(E,v(dagger)) and He + ICl(beta,v(dagger)) potentials, the transition energies of the observed features permit the relative binding energies of the T-shaped and linear ground-state He...ICl(X,v(") = 0) conformers to be accurately measured. The binding energies of the T-shaped and linear He...I(35)Cl(X,v(") = 0) conformers are 16.6(3) and 22.0(2) cm(-1), respectively. These values and the observed transition energies are then used to set the binding energies of the T-shaped He...I(35)Cl complexes in the He + ICl(A,v(') = 15), He + ICl(B,v(') = 3), He + ICl(beta,v(dagger) = 1), and He + ICl(E,v(dagger) = 12) potentials as 13.4(3), 13.3(3), 41(1), and 39.2(4) cm(-1), respectively. Nonadiabatic coupling between specific intermolecular vibrational levels within the He + ICl(beta,v(dagger)) state and the ICl(D('),v(dagger)) molecular state is observed.
Related Concept Videos
Molecular Geometry and Dipole Moments
Van der Waals Interactions
Intermolecular Forces
Intermolecular Forces
The Van der Waals Equation
Van der Waals Equation
First, the attractive forces between molecules, which are stronger at higher densities and reduce the pressure, are considered by adding to the pressure a term equal to the square of the molar density multiplied by a positive coefficient a. Second, the volume...


