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The field therefore has applications to a wide variety of more specialized fields, including electro- and photochemistry, polymer and supramolecular chemistry, and bioorganic chemistry, enzymology, and chemical biology, as well as to commercial enterprises involving process chemistry, chemical engineering, materials science and nanotechnology, and drug discovery. Physical organic chemistry is the study of the relationship between structure and reactivity of organic molecules. More specifically, physical organic chemistry applies the experimental tools of physical chemistry to the study of the structure of organic molecules and provides a theoretical framework that interprets how structure influences both mechanisms and rates of organic reactions. It can be thought of as a subfield that bridges organic chemistry with physical chemistry. Physical organic chemists use both experimental and theoretical disciplines such as spectroscopy, spectrometry, crystallography, computational chemistry, and quantum theory to study both the rates of organic reactions and the relative chemical stability of the starting materials, transition states, and products. This includes experiments to measure or determine the enthalpy (. Chemists may use various chemical and mathematical analyses, such as a Van 't Hoff plot, to calculate these values. Empirical constants such as bond dissociation energy, standard heat of formation (. For complex molecules, a . This type of analysis is often referred to as Benson group increment theory, after chemist Sidney Benson who spent a career developing the concept. Group increment data are available for radical systems. Physical organic chemists use conformational analysis to evaluate the various types of strain present in a molecule to predict reaction products. The A- value is the difference in the Gibbs' free energy between the axial and equatorial forms of substituted cyclohexane, and by adding together the A- values of various substituents it is possible to quantitatively predict the preferred conformation of a cyclohexane derivative. In addition to molecular stability, conformational analysis is used to predict reaction products. One commonly cited example of the use of conformational analysis is a bi- molecular elimination reaction (E2). This reaction proceeds most readily when the nucleophile attacks the species that is antiperiplanar to the leaving group. A molecular orbital analysis of this phenomenon suggest that this conformation provides the best overlap between the electrons in the R- H . Such interactions include, but are not limited to, hydrogen bonding, electrostatic interactions between charged molecules, dipole- dipole interactions, polar- . In addition, the hydrophobic effect. The precise physical origin of the hydrophobic effect originates from many complex interactions, but it is believed to be the most important component of biomolecular recognition in water. The study of non- covalent interactions is also used to study binding and cooperativity in supramolecular assemblies and macrocyclic compounds such as crown ethers and cryptands, which can act as hosts to guest molecules. Acid. Organic chemists are primarily concerned with Br. Chemists use a series of factors developed from physical chemistry - - electronegativity/Induction, bond strengths, resonance, hybridization, aromaticity, and solvation. In general, interactions between molecules of the same type are preferred. That is, hard acids will associate with hard bases, and soft acids with soft bases. The concept of hard acids and bases is often exploited in the synthesis of inorganic coordination complexes. Kinetics. Unlike thermodynamics, which is concerned with the relative stabilities of the products and reactants (. Chemists have also used the principle of thermodynamic versus kinetic control to influence reaction products. Rate laws. The rate law provides a quantitative relationship between the rate of a chemical reaction and the concentrations or pressures of the chemical species present. The experimentally determined rate law refers to the stoichiometry of the transition state structure relative to the ground state structure. Determination of the rate law was historically accomplished by monitoring the concentration of a reactant during a reaction through gravimetric analysis, but today it is almost exclusively done through fast and unambiguous spectroscopic techniques. In most cases, the determination of rate equations is simplified by adding a large excess (. A catalyst participates in the chemical reaction but is not consumed in the process. Catalysts may also influence a reaction rate by changing the mechanism of the reaction. Isotopic substitution changes the potential energy of reaction intermediates and transition states because heavier isotopes form stronger bonds with other atoms. Atomic mass affects the zero- point vibrational state of the associated molecules, shorter and stronger bonds in molecules with heavier isotopes and longer, weaker bonds in molecules with light isotopes. Substituents can exert an effect through both steric and electronic interactions, the latter of which include resonance and inductive effects. The polarizability of molecule can also be affected. Most substituent effects are analyzed through linear free energy relationships (LFERs). The most common of these is the Hammett Plot Analysis. The parameters of the Hammett plots are sigma (. Therefore, two new scales were produced that evaluate the stabilization of localized charge through resonance. Hammett analysis can be used to help elucidate the possible mechanisms of a reaction. For example, if it is predicted that the transition state structure has a build- up of negative charge relative to the ground state structure, then electron- donating groups would be expected to increase the rate of the reaction. Steric and polar effects are analyzed through Taft Parameters. Changing the solvent instead of the reactant can provide insight into changes in charge during the reaction. The Grunwald- Winstein Plot provides quantitative insight into these effects. A change in solvent can also allow a chemist to influence the thermodynamic or kinetic control of the reaction. Reactions proceed at different rates in different solvents due to the change in charge distribution during a chemical transformation. Solvent effects may operate on the ground state and/or transition state structures. In non- polar aprotic solvents, the enol form is strongly favored due to the formation of an intramolecular hydrogen- bond, while in polaraprotic solvents, such as methylene chloride, the enol form is less favored due to the interaction between the polar solvent and the polar diketone. However, the faster rate of cis- trans isomerization in THF results in a loss of stereochemical purity. This is a case where understanding the effect of solvent on the stability of the molecular configuration of a reagent is important with regard to the selectivity observed in an asymmetric synthesis. Quantum chemistry. Due to these limitations, a true understanding of physical organic chemistry requires a more rigorous approach grounded in particle physics. Quantum chemistry provides a rigorous theoretical framework capable of predicting the properties of molecules through calculation of a molecule. Particles are defined by their associated wavefunction, an equation which contains all information associated with that particle. This information is extracted from the wavefunction through the use of mathematical operators. Time- independent Schr. In the various forms of the Schr. For this reason, nuclei are of negligible size in relation to much lighter electrons and are treated as point charges in practical applications of quantum chemistry. Due to complex interactions which arise from electron- electron repulsion, algebraic solutions of the Schr. In systems with multiple electrons, an overall multielectron wavefunction describes all of their properties at once. Such wavefunctions are generated through the linear addition of single electron wavefunctions to generate an initial guess, which is repeatedly modified until its associated energy is minimized. 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