Hollow-core photonic-crystal fibers are shown to offer the unique possibility of coherent excitation and probing of Raman-active vibrations in molecules by isolated air-guided modes of electromagnetic radiation. A 3-cm section of a hollow photonic-crystal fiber is used to prepare isolated air-guided modes of pump and probe fields for a coherent excitation of 2331-cm −1 Q-branch vibrations of molecular nitrogen in the gas filling the fiber core, enhancing coherent anti-Stokes Raman scattering through these vibrations by a factor of 15 relative to the regime of tight focusing.Coherent Raman excitations is one of the most important pathways of laser-matter interactions. Coherent Raman processes are at the heart of many efficient spectroscopic [1,2] and microscopic [3] techniques, methods of frequency conversion [4] and time-resolved studies [5,6], as well as lasercooling [7] and quantum-control [8] schemes. Multiple Raman sidebands produced through high-order stimulated Raman scattering allow few-field-cycle pulses to be synthesized [9]. The potential of nonlinear Raman techniques has been recently enhanced by coherent control approaches [10].Many interesting possibilities of coherent Raman processes are associated with waveguide regimes of Raman excitation [11,12]. Hollow fibers [13,14] and Bragg planar waveguides [15] have been shown to improve the efficiency of coherent anti-Stokes Raman scattering (CARS) in the gas phase. Large nonlinear interaction lengths make hollow fibers filled with a Raman-active gas efficient generators of sub-4-fs pulses [9].Air-guided modes in standard hollow fibers are, however, leaky, with the magnitude of losses scaling as 2 / a 3 with the fiber inner radius a and the radiation wavelength [16], which dictates the choice of hollow fibers with a ϳ 50-300 m for nonlinear-optical experiments. Such large-a fibers are essentially multimode, with many guided modes typically contributing to nonlinear-optical interactions [14,17]. This multimode nature of nonlinear-optical processes complicates a precise calibration of the coherent Raman signal as a function of the concentration of Ramanactive species, leads to unwanted interference phenomena in spectroscopic and time-resolved coherant Raman measurements, and should be one of the factors limiting the duration of ultrashort pulses synthesized in hollow fibers.The number of air-guided modes can be radically reduced by using hollow-core photonic-crystal fibers (PCFs) [18,19]. Such fibers guide light due to the high reflectivity of a twodimensionally periodic (photonic-crystal) cladding (the inset in Fig. 1) within photonic band gaps. Low-loss guiding in a few or even a single air-guided mode can be implemented under these conditions in a hollow core with a typical diameter of 10-20 m [18][19][20]. Hollow PCFs with such core diameters have been recently demonstrated to enhance nonlinear-optical processes, including stimulated Raman scattering [21], four-wave mixing (FWM) [22], and selfphase modulation [23]. Air-guided modes in hollow PCFs can sup...