Valence Bond Study of the Hydrogen Bond. I

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Abstract
A valence bond calculation for the four electrons involved in the straight hydrogen bond O–H…O without excess charges is performed nonempirically. Five valence bond structures proposed by Tsubomura are adopted, i. e. , (I) O–H O, (II) O - H + O, (III) O + H - O, (IV) O - H–O + and (V) OH - O + . The calculations are done for both trigonal and tetrahedral hybrid atomic orbitals of oxygen atoms. The adiabatic potential of the proton is calculated as a function of the O…O and the O–H distances. The shifts of the equilibrium O–H distance and of the O–H frequency with the formation of the hydrogen bond are studied. When different orbital exponents are used in the atomic orbitals of O, O - and O + , and H and H - , according to Slater's rule, the obtained shifts agree qualitatively with experiment, although the absolute values deviate from experimental ones in the short hydrogen bond.

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