This technique involves the phenomenon of wave mixing, takes advantage of the high intensity of stimulated Raman scattering, and has the applicability of conventional Raman spectroscopy. In the CARS method two strong collinear laser beams at frequencies ν₁ and ν₂ (ν₁ > ν₂) irradiate a sample. If the frequency difference, ν₁ − ν₂, is equal to the frequency of a Raman-active rotational or vibrational transition ν_R, then the efficiency of wave mixing is enhanced and signals at ν_A = 2ν₁ − ν₂ (anti-Stokes) and ν_S = 2ν₂ − ν₁ (Stokes) are produced by wave mixing due to the nonlinear polarization of the medium. While either output signal may be detected, the anti-Stokes frequency is well above ν₁ and has the advantage of being readily separated by optical filtering from the incident beams and fluorescence that may be simultaneously generated in the sample. Although the same spectroscopic transitions, namely, those with frequencies ν_R, are determined from both conventional Raman spectroscopy and CARS, the latter produces signals that have intensities 10⁴–10⁵ times as great. This enhanced signal level can greatly reduce the time necessary to record a spectrum. Because of the coherence of the generated signals, the divergence of the output beam is small, and good spatial discrimination against background signals is obtained. Such noise may occur in the examination of molecules undergoing chemiluminescence or existing in either flames or electric discharges. Since the generation of the anti-Stokes signal occurs in a small volume where the two incident beams are focused, sample size does not have to be large. Microlitre-size liquid samples and gases at millitorr pressures can be used. Another advantage of the spatial discrimination available is the ability to examine different regions within a sample. For example, CARS can be used to determine the composition and local temperatures in flames and plasmas. Because of the near collinearity of the exciting and observing signals, the Doppler effect is minimized and resolution of 0.001 cm⁻¹ can be achieved. The primary disadvantage of the technique is the need for laser sources with excellent intensity stabilization.

Laser magnetic resonance and Stark spectroscopies

Because of the nature of laser-signal generation, most lasers are not tunable over an appreciable frequency range and even those that can be tuned, such as dye lasers, must be driven by a pump laser and for a given dye have a limited tuning range. This limitation can be overcome for molecules that possess permanent magnetic moments or electric dipole moments by using external magnetic or electric fields to bring the energy spacing between levels into coincidence with the frequency of the laser.

Molecules that have one or more unpaired electrons will possess permanent magnetic moments. Examples of such paramagnetic systems are free radicals such as NO, OH, and CH₂ and transition-metal ions like Fe(H₂O)₆³⁺ and Cr(CN)₆⁴⁻. A hypothetical electronic energy-level diagram for a radical having a single unpaired electron and two energy levels, a ground state having zero orbital angular momentum (L = 0), and an excited state with L = 1 is shown in Figure 11. When the magnetic field is increased, the separation of the Zeeman components will shift, and each allowed transition (ΔM = 0 or ±1, where M = L + M_S [spin angular momentum]) will progressively come into coincidence with the laser frequency and a change in signal intensity will be observed. To enhance the sensitivity of this technique, the sample is often placed inside the laser cavity, and the magnetic field is modulated. By making the laser cavity part of a reacting flow system, the presence of paramagnetic reaction intermediates can be detected and their spectra recorded. Concentrations of paramagnetic species as low as 10⁹ molecules per cubic centimetre have been observed. This method has made it possible to identify radicals observed in interstellar space and to provide spectral detail for them.

An analogous method, called Stark spectroscopy, involves the use of a strong variable electric field to split and vary the spacing of the energy levels of molecules that possess a permanent electric dipole moment. The general principle is embodied in Figure 11, with the substitution of an electric field for the magnetic field. Since very high fields (1,000–5,000 volts per centimetre) are required, the sample must be located between closely spaced metal plates. This precludes the inclusion of the sample inside the laser cavity. Sensitivity is enhanced by modulating the electric field. Although the frequency of the laser can be stabilized and measured to within 20–40 kilohertz, the determination of molecular parameters is limited to the accuracy inherent in the measurement of the electric field—namely, one part in 10⁴. This method is useful for the determination of the dipole moment and structure of species whose rotational transitions fall above the microwave region.