The three fundamental vibrations of the water molecule

ν₁,O-H symmetric stretching
3657 cm⁻¹ (2.734 μm)

ν₂, H-O-H bending
1595 cm⁻¹ (6.269 μm)

ν₃, O-H asymmetric stretching
3756 cm⁻¹ (2.662 μm)

 

The water molecule has three fundamental molecular vibrations. The O-H stretching vibrations give rise to absorption bands with band origins at 3657 cm⁻¹ (ν₁, 2.734 μm) and 3756 cm⁻¹ (ν₃, 2.662 μm) in the gas phase. The asymmetric stretching vibration, of B₂ symmetry in the point group C_2v is a normal vibration. The H-O-H bending mode origin is at 1595 cm⁻¹ (ν₂, 6.269 μm). Both symmetric stretching and bending vibrations have A₁ symmetry, but the frequency difference between them is so large that mixing is effectively zero. In the gas phase all three bands show extensive rotational fine structure.^[14] In the Near-infrared spectrum ν₃ has a series of overtones at wavenumbers somewhat less than n·ν₃, n=2,3,4,5… Combination bands, such as ν₂ + ν₃ are also easily observed in the near-infrared region.^[15][16] The presence of water vapor in the atmosphere is important for atmospheric chemistry especially as the infrared and near infrared spectra are easy to observe. Standard (atmospheric optical) codes are assigned to absorption bands as follows. 0.718 μm (visible): α, 0.810 μm: μ, 0.935 μm: ρστ, 1.13 μm: φ, 1.38 μm: ψ, 1.88 μm: Ω, 2.68 μm: X. The gaps between the bands define the infrared window in the Earth’s atmosphere.^[17]

The infrared spectrum of liquid water is dominated by the intense absorption due to the fundamental O-H stretching vibrations. Because of the high intensity, very short path lengths, usually less than 50 μm, are needed to record the spectra of aqueous solutions. There is no rotational fine structure, but the absorption bands are broader than might be expected, because of hydrogen bonding.^[18] Peak maxima for liquid water are observed at 3450 cm⁻¹ (2.898 μm), 3615 cm⁻¹ (2.766 μm) and 1640 cm ⁻¹ (6.097 μm).^[14] Direct measurement of the infrared spectra of aqueous solutions requires that the cuvette windows be made of substances such as calcium fluoride which are water-insoluble. This difficulty can alternatively be overcome by using an attenuated total reflectance (ATR) device rather than transmission.

In the near-infrared range liquid water has absorption bands around 1950 nm (5128 cm⁻¹), 1450 nm (6896 cm⁻¹), 1200 nm (8333 cm⁻¹) and 970 nm, (10300 cm⁻¹).^[19][20][15] The regions between these bands can be used in near-infrared spectroscopy to measure the spectra of aqueous solutions, with the advantage that glass is transparent in this region, so glass cuvettes can be used. The absorption intensity is weaker than for the fundamental vibrations, but this is not important as longer path-length cuvettes can be used. The absorption band at 698 nm (14300 cm⁻¹) is a 3rd overtone (n=4). It tails off onto the visible region and is responsible for the intrinsic blue color of water. This can be observed with a standard UV/vis spectrophotometer, using a 10 cm path-length. The colour can be seen by eye by looking through a column of water about 10 m in length; the water must be passed through an ultrafilter to eliminate color due to Rayleigh scattering which also can make water appear blue.^[16][21][22]

The spectrum of ice is similar to that of liquid water, with peak maxima at 3400 cm⁻¹ (2.941 μm), 3220 cm⁻¹ (3.105 μm) and 1620 cm⁻¹ (6.17 μm)^[14]

In both liquid water and ice clusters, low-frequency vibrations occur, which involve the stretching (TS) or bending (TB) of intermolecular hydrogen bonds (O–H•••O). Bands at wavelengths λ = 50-55 μm or 182-200 cm⁻¹ (44 μm, 227 cm⁻¹ in ice) have been attributed to TS, intermolecular stretch, and 200 μm or 50 cm⁻¹ (166 μm, 60 cm⁻¹ in ice), to TB, intermolecular bend^[11]

Absorption coefficients for 200 nm and 900 nm are almost equal at 6.9 m⁻¹ (attenuation length of 14.5 cm). Very weak light absorption, in the visible region, by liquid water has been measured using an integrating cavity absorption meter (ICAM).^[16] The absorption was attributed to a sequence of overtone and combination bands whose intensity decreases at each step, giving rise to an absolute minimum at 418 nm, at which wavelength the attenuation coefficient is about 0.0044 m⁻¹, which is an attenuation length of about 227 meters. These values correspond to pure absorption without scattering effects. The attenuation of, e.g., a laser beam would be slightly stronger.

Visible light absorption spectrum of pure water (absorption coefficient vs. wavelength)^[16][21][22]

The electronic transitions of the water molecule lie in the vacuum ultraviolet region. For water vapor the bands have been assigned as follows.^[11]

• 65 nm band — many different electronic transitions, photoionization, photodissociation
• discrete features between 115 and 180 nm
  • set of narrow bands between 115 and 125 nm
    Rydberg series: 1b₁ (n₂) → many different Rydberg states and 3a₁ (n₁) → 3sa₁ Rydberg state
  • 128 nm band
    Rydberg series: 3a₁ (n₁) → 3sa₁ Rydberg state and 1b₁ (n₂) → 3sa₁ Rydberg state
  • 166.5 nm band
    1b₁ (n₂) → 4a₁ (σ₁*-like orbital)

At least some of these transitions result in photodissociation of water into H+OH. Among them the best known is that at 166.5 nm.