The
strong absorption of liquid water in the infrared (IR) molecular
fingerprint region constitutes a challenge for applications of vibrational
spectroscopy in chemistry, biology, and medicine. While high-power
IR laser sources enable the penetration of ever thicker aqueous samples,
thereby mitigating the detrimental effects of strong attenuation on
detection sensitivity, a basic advantage of heterodyne-measurement-based
methods hasto the best of our knowledgenot been harnessed
in broadband IR measurements to date. Here, employing field-resolved
spectroscopy (FRS), we demonstrate in theory and experiment fundamental
advantages of techniques whose signal-to-noise ratio (SNR) scales
linearly with the electric field over those whose SNR scales linearly
with radiation intensity, including conventional Fourier-transform
infrared (FTIR) and direct absorption spectroscopy. Field-scaling
brings about two major improvements. First, it squares the measurement
dynamic range. Second, we show that the optimum interaction length
with samples for SNR-maximized measurements is twice the value usually
considered to be optimum for FTIR devices. In order to take full advantage
of these properties, the measurement must not be significantly affected
by technical noise, such as intensity fluctuations, which are common
for high-power sources. Recently, it has been shown that subcycle,
nonlinear gating of the molecular fingerprint signal renders FRS robust
against intensity noise. Here, we quantitatively demonstrate this
advantage of FRS for thick aqueous samples. We report sub-μg/mL
detection sensitivities for transmission path lengths up to 80 μm
and a limit of detection in the lower μg/mL range for transmission
paths as long as 200 μm.