Fourier-transform sum-frequency surface vibrational spectroscopy with femtosecond pulses

The Discrete Fourier Transform (DFT) is a fundamental tool in signal processing, extending the discrete-time Fourier transform by evaluating discrete signals at uniformly spaced frequency intervals. This transformation converts a finite sequence of time-domain samples into frequency components, each representing complex sinusoids ordered by frequency. The DFT translates these sequences into the frequency domain, effectively indicating the magnitude and phase of each frequency component present...

A pulse is a short burst of radio waves distributed over a range of frequencies that simultaneously excites all the nuclei in the sample. Upon passing a radio frequency pulse along the x-axis, the nuclei absorb energy corresponding to their Larmor frequencies and achieve resonance. This shifts the net magnetization vector from the z-axis toward the transverse plane. This angle of rotation of the magnetization vector, or the flip angle, is proportional to the duration and intensity of the pulse.

When Infrared (IR) radiation passes through a covalently bonded molecule, the bonds transition from lower to higher vibrational levels. The fundamental vibrational motions that result in infrared absorption can be classified as stretching or bending vibrations.
Stretching vibrations are vibrational motions that occur along the bond line, changing the bond length or distance between two bonded atoms. They are further distinguished as symmetric or asymmetric. In symmetric stretching, the...

The Fourier series is instrumental in representing periodic functions, offering a powerful method to decompose such functions into a sum of sinusoids. This technique, however, necessitates modification when applied to nonperiodic functions. Consider a pulse-train waveform consisting of a series of rectangular pulses. When these pulses have a finite period, they can be accurately represented by a Fourier series. Yet, as the period approaches infinity, resulting in a single, isolated pulse, the...

The Fourier Transform is a pivotal mathematical tool in signal processing, enabling the transformation of time-domain signals into their frequency-domain representations. Among the numerous elements within this domain, certain functions like the sinc function, delta function, and exponential signals hold significant importance due to their unique properties and implications.
The sinc function, defined as sinc(x) = sin(πx)/(πx), is particularly notable for its symmetry and behavior at zero. It...

Identical bonds within a polyatomic group can stretch symmetrically (in-phase) or asymmetrically (out-of-phase). Similar to hydrogen bonding, these vibrations also influence the shape of the IR peak. Generally, asymmetric stretching frequencies are higher than symmetric stretching frequencies. For example, primary amines exhibit two distinct IR peaks between 3300–3500 cm−1 corresponding to the symmetric and asymmetric N-H stretching, while secondary amines exhibit a single stretching vibration...