Interfaces play a crucial role in the exchange of energy and matter in various physical, chemical and biological systems. A particular interest has been to study interfaces between aqueous phases and various minerals because of their importance in understanding geochemical phenomena as well as for applications such as enhanced oil recovery. The nonlinear optical technique of vibrational sum-frequency generation (SFG) spectroscopy, introduced over 20 years ago, has become a powerful tool to investigate various surfaces, in particular, mineral-water interfaces. One of the challenges of the SFG spectroscopy of aqueous surfaces is the need to tune the central frequency of relatively narrowband IR lasers through the broad range of the OH-stretch frequencies of water molecules (3000 - 4000 cm-1). We have developed a novel ultrabroadband IR laser source that generates infrared pulses in the ~2800-6000 cm-1 range (lambda~3300-1800 nm) with bandwidths Delta(nu)>1000 cm-1, and bandwidths >2000 cm-1 in the near-IR range (lambda~1000-2000 nm). Pulse front tilt of signal pulse has been corrected allowing for compression of signal pulses down to 25 fsec. Such ultrabroadband IR pulses allow us to perform SFG spectroscopy of aqueous surfaces over the entire frequency range of water molecule spectrum (extending from ~2900 cm -1 to ~3800 cm -1) simultaneously, without tuning the laser ("in one shot"). We have used this novel ultrabroadband IR source to investigate the vibrational SFG spectra of silica/water interfaces. The high signal-to-noise ratio of our spectroscopic setup has allowed us to study low-intensity features that were not studied in detail, or recognized previously in the SFG-spectroscopy investigations, including: 1) non-hydrogen bonded OH vibrations at hydrophilic silica/water interfaces; 2) combination [stretch+bend] bands of water at the silica surface appearing at ~5000-5200 cm -1. 3) Overtones of water stretching modes at silica/water interfaces. The most important conclusions from these studies are outlined below. 1. Non-hydrogen bonded hydroxyls at silica/water interface. Typically SFG-studies of mineral/water interfaces (in particular, silica/water) have focused on the most pronounced features - peaks of H-bonded hydroxyls at ~3150 and ~3450 cm -1. We have been able to systematically observe and study a weaker peak at ~3670 - 3700 cm -1. This peak becomes more pronounced as the pH of aqueous phase decreases, as well as the ionic strength increases, indicating that the hydroxyls corresponding to this spectral feature are situated in a very close proximity to the surface. Isotopic dilution experiments indicate that the 3700 cm -1 feature is not due to asymmetric OH stretches as was suggested before. Based on our results, we suggest that this spectral feature corresponds to hydroxyls of water molecules at the silica surface that cannot hydrogen bond with silanol groups because of the lower density of silanols compared to H2O. We believe this to be the first surface-specific study of non-hydrogen bonded hydroxyls at silica, a surface widely accepted as hydrophilic. 2. SFG spectroscopy of [ν(OH)+δ(HOH)] combination bands of water at silica surface. We have extended SFG spectroscopy of the interfacial hydroxyls at mineral/water surfaces into the near-IR frequency range. The studies of overtones of interfacial OH(OD) groups will provide information on the anharmonicity of such species, and thus on the energy of dissociation. In addition, the positions of the overtone frequencies of the hydroxyls are more sensitive to interactions with the environment than the fundamental stretch frequencies. Our particular focus has been to study the stretch+bend combination band nu comb nu;(OH)+delta;(HOH) of liquid water which occurs in the near-IR spectral range at ~5000-5200 cm -1. It is typically much weaker in the FTIR absorption spectra than the fundamental transitions of the OH stretches or HOH bending, similar to overtones of these modes. We have performed, what we believe to be, the first surface-specific vibrational SFG spectroscopic measurements of combination bands of water molecules at silica surfaces. SFG spectroscopy of water combination band allows access to the water bending mode (delta~1600 cm -1), which still has not been observed in sum-frequency. / Chemistry