Introduction to nuclear magnetic resonance spectroscopy

Introduction

Nuclear magnetic resonance spectroscopy (NMR) is a widely used and powerful method that takes advantage of the magnetic properties of certain nuclei. The basic principle behind NMR is that some nuclei exist in specific nuclear spin states when exposed to an external magnetic field. NMR observes transitions between these spin states that are specific to the particular nuclei in question, as well as that nuclei's chemical environment. However, this only applies to nuclei whose spin, I, is not equal to 0, so nuclei where I = 0 are ‘invisible’ to NMR spectroscopy. These properties have led to NMR being used to identify molecular structures, monitor reactions, study metabolism in cells, and is used in medicine, biochemistry, physics, industry, and almost every imaginable branch of science.

Theory

The chemical theory that underlies NMR spectroscopy depends on the intrinsic spin of the nucleus involved, described by the quantum number S. Nuclei with a non-zero spin are always associated with a non-zero magnetic moment, as described by [link] , where μ is the magnetic moment, S is the spin, and γ is always non-zero. It is this magnetic moment that allows for NMR to be used; therefore nuclei whose quantum spin is zero cannot be measured using NMR. Almost all isotopes that have both an even number of protons and neutrons have no magnetic moment, and cannot be measured using NMR.

In the presence of an external magnetic field (B) for a nuclei with a spin I = ¹ / ₂ , there are two spin states present of + ¹ / ₂ and - ¹ / ₂ . The difference in energy between these two states at a specific external magnetic field (B _x ) are given by [link] , and are shown in [link] , where E is energy, I is the spin of the nuclei, and μ is the magnetic moment of the specific nuclei being analyzed. The difference in energy shown is always extremely small, so for NMR strong magnetic fields are required to further separate the two energy states. At the applied magnetic fields used for NMR, most magnetic resonance frequencies tend to fall in the radio frequency range.

The reason NMR can differentiate between different elements and isotopes is due to the fact that each specific nuclide will only absorb at a very specific frequency. This specificity means that NMR can generally detect one isotope at a time, and this results in different types of NMR: such as ¹ H NMR, ¹³ C NMR, and ³¹ P NMR, to name only a few.

The subsequent absorbed frequency of any type of nuclei is not always constant, since electrons surrounding a nucleus can result in an effect called nuclear shielding, where the magnetic field at the nucleus is changed (usually lowered) because of the surrounding electron environment. This differentiation of a particular nucleus based upon its electronic (chemical) environment allows NMR be used to identify structure. Since nuclei of the same type in different electron environments will be more or less shielded than another, the difference in their environment (as observed by a difference in the surrounding magnetic field) is defined as the chemical shift.