% http://scifun.chem.wisc.edu/Thesis_Awards/chapter_guidelines.html \chapter{Public} \section{Chemical systems} % --------------------------------------------------------------------- Chemical systems are complex! % They contain many molecules ($10^{25}$ in a cup of coffee, 1 trillion in each human cell). % These molecules have multiple interaction modes, both internal (intramolecular) and external (intermolecular). % The reactivity of the system taken as a whole can be dominated by very rare but very important species, \textit{e.g.} catalysts. % Despite this complexity, scientists have gotten very good at describing chemical systems through representations of dynamic equilibrium. % In such situations, several key parameters emerge: % \begin{itemize} \item concentration \item timescale (rate) \item lengthscale \end{itemize} \subsection{Concentration} \subsection{Timescale} % TODO: dynamics in chemical systems: collision time, dephasing, rotation, relaxation, diffusion... \subsection{Lengthscale} \section{Analytical chemistry} % ----------------------------------------------------------------- Traditionally, chemists have seen fit to divide themselves into four specializations: analytical, inorganic, organic, and physical. % In recent years, materials chemistry and chemical biology have become specializations in their own right. % This dissertation focuses on analytical chemistry. % Analytical chemists separate, identify, and quantify chemical systems. % To do this, we build instruments that exploit physical properties of the chemical components: % \begin{itemize} \item separation science (chromatography, electrophoresis) \item mass spectrometry \item electrochemistry \item microscopy \item spectroscopy \end{itemize} Spectroscopy is a family of strategies that exploit the interaction of chemical systems with light. % \section{Spectroscopy} % ------------------------------------------------------------------------- Molecules respond to electric fields. % Static electric fields cause charged molecules (ions) to move, as in electrophoresis and mass spectrometry. % Oscillating electric fields, also known as light, can interact directly with the molecules themselves, driving transitions. % However, these transitions can only be driven with the appropriate frequency of light (resonance). % Different frequencies (colors) of light interact with different kinds of transitions, revealing different features of the molecule of interest. % % TODO: different energy ranges / transition types (nuclear, rotational, vibrational, electronic) % TODO: how is a photon created or absorbed? \subsection{Nonlinear spectroscopy} Spectroscopy is fantastic, but sometimes simple experiments don't reveal everything. % Nonlinear spectroscopy uses multiple electric fields simultaniously, revealing even more information about the chemical system. % % TODO: simple graphic of homogeneous vs inhomogeneous broadening % TODO: 2D freq-freq with increasing inhomogeneity (from Dan's theory work) \section{Instrumentation} % ---------------------------------------------------------------------- To accomplish nonlinear spectroscopy, specialized light sources are needed: % \begin{itemize} \item gigantic electric fields \item ultrafast time resoution \item tunable frequencies \end{itemize} \subsection{LASER} These sources are made using Light Amplified by the Stimulated Emission of Radiation (LASER). % % TODO: discussion of the original LASER, basic LASER physics % TODO: discuss temporal coherence % TODO: discuss pulsed sources By keeping a wide range ofr colors in phase simulatniously, we are able to create truly ultrafast pulses of light. % The work presented in this dissertation was primarily taken using a 35 fs 1 KHz system. % 35 fs ($35\times10^{15}$ second) pulses are incredibly short: \begin{equation} \frac{\text{pulse duration (35 fs)}}{\text{time between pulses (1 ms)}} \approx \frac{\text{5.75 months}}{\text{age of universe (13.7 billion years)}} % TODO: cite age \end{equation} proportionally, our sample spends 6 months in the ``sun'' for every age of the unverse in the dark. % Because all of the energy within the pulse is compressed to such a short period of time, these pulses are also incredibly powerful: \begin{equation} \frac{\text{energy per pulse (4 mJ)}}{\text{pulse duration (35 fs)}} \approx \frac{\text{US electricity generation} (5.43\times10^{11} W)}{5} % TODO: cite generation \end{equation} this laser outputs electric fields one fifth as powerful as total US electricity generation (2016). % TODO: pulses are very thin (draw circle, use thickness of paper) to motivate 'hard to handle' \subsection{OPA} % https://osf.io/vwhjk/