  The constitutive laws of hydrogen bonds (H-bonds) are central to
understanding microphysical processes not precisely observed, especially in
terms of structural properties. Previous experiences in water H-bonding
revealed that as the intermolecular O...O distance shortens, the O-H stretching
frequency redshifts; thus, an elongated O-H bond length can be empirically
inferred, which is described as the constitutive law under the cooperative
effect. Here, using the high-precision CCSD(T) method, we report a violation of
the conventional constitutive law in water dimer. That is, when the variation
in the O...O distance changes from stretching by 0.06 to contracting by -0.15
angstrom compared to the equilibrium position, the donor O-H bond length
decreases from 0.9724 to 0.9717 angstrom, and the O-H stretching frequency
redshifts from 3715 to 3708 cm-1. Our work highlights that the O-H bond length
decreases simultaneously with its stretching frequency, which is clearly
inconsistent with the previously recognized constitutive law.
