We begin with the proton-electron model. This model predictsthat the covalent bond is more strongly preferred in the condensed statewhen there are stronger Coulomb interactions and lower orbital energies.The increased Coulomb interactions occur because the electronsof a central atom are more tightly bound to the nucleus than the electrons onthe periphery of the molecule. The increased kinetic energy of theelectron orbitals produced by this tighter binding is manifested in highervalence electronic shells. The energy of the shell is directlyrelated to the Rydberg energy, which in turn is directly related to theeffective polarizability. Higher valence shells are stable if theeffective polarizability is high enough and the Rydberg energy is lowenough. It is therefore reasonable to look at the bond angles ofproton-electron motion to explain trends in bond angles in condensedphase systems.
In this model, the bond angle is closely related to the orientationof the induced dipoles from the central atom to the peripheral atoms. Themagnitude of these dipoles is directly related to the size of the orbitalpolarizability (the effective polarizability for the electronin the molecular orbital). As the orbital polarizability increases, so does thedipole moment, which in turn increases the energy of the Rydbergstate. This repulses the electrons further from the nucleus, whichincreases the orbital energy, which, in turn, lowers the Rydbergenergy, which increases the magnitude of the induced dipole. Once themomentum is balanced, the dipole is stabilized. Clearly, this model isconfined to the condensed phase.
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