Electronic density Fukui function

The same procedure can be applied for derivatives from other representations. Electronic properties obtained by differentiation are usually classified by its dependence on the position. Global properties have the same value everywhere, such as the chemical potential, hardness and softness. Electron density, Fukui function and local softness change throughout the molecule, and they are called local properties. Finally, kernel properties depend on two or more position vectors, like the density response and softness kernels. Global parameters describe molecular reactivity, local properties provide information on site selectivity, while kernels can be used to understand site activation. 

The positive sign of chemical hardness is a consequence of the concavity of the energy with respect to the number of electrons. The Fukui function, /(r), appears in both equations since it represents the sensitivity of the chemical potential to the changes in the external potential and that of the density with respect to the number of electrons,6... 

Popular qualitative chemical concepts such as electronegativity [1] and hardness [2] have been widely used in understanding various aspects of chemical reactivity. A rigorous theoretical basis for these concepts has been provided by density functional theory (DFT). These reactivity indices are better appreciated in terms of the associated electronic structure principles such as electronegativity equalization principle (EEP), hard-soft acid-base principle, maximum hardness principle, minimum polarizability principle (MPP), etc. Local reactivity descriptors such as density, Fukui function, local softness, etc., have been used successfully in the studies of site selectivity in a molecule. Local variants of the structure principles have also been proposed. The importance of these structure principles in the study of different facets of medicinal chemistry has been highlighted. Because chemical reactions are actually dynamic processes, time-dependent profiles of these reactivity descriptors and the dynamic counterparts of the structure principles have been made use of in order to follow a chemical reaction from start to finish. 

The Fukui function is normalized 4=1 [9]). This follows from the normalization condition for the electron density distribution function ... 

Senet, P. (1996). NonUnear electronic responses, Fukui functions and hardnesses as functionals of the ground-state electronic density. J. Chem. Phys. 105,6471-6490. 

A reaction will in general involve a change in the electron density, which may be quantified in terms of the Fukui function. ... 

The Fukui function indicates the change in the electron density at a given position when the number of electrons is changed. We may define two finite difference versions of the function, corresponding to addition or removal of an electron. 

Besides the already mentioned Fukui function, there are a couple of other commonly used concepts which can be connected with Density Functional Theory (Chapter 6). The electronic chemical potential p is given as the first derivative of the energy with respect to the number of electrons, which in a finite difference version is given as half the sum of the ionization potential and the electron affinity. Except for a difference in sign, this is exactly the Mulliken definition of electronegativity. ... 

It is important to mention that the chemical potential and the hardness, p, and 17, are global-type response functions that characterize the molecule as a whole, while the electronic density p(r), the Fukui function fir), and the dual descriptor A/(r) are local-type response functions whose values depend upon the position within the molecule. 

For the second derivative of the electronic density with respect to the number of electrons, the dual descriptor, one can proceed as in the case of the energy. That is, the Fukui function using the Heaviside function [25] is written as... 

Now, the Fukui function is closely related to the frontier orbitals. This can be seen from Equations 2.29 and 2.30, together with Equation 2.42, because if one determines the electron densities of the iV0 — 1- and the N() + 1-electron systems with the orbitals set corresponding to the Mj-electron system, then... 

The Fukui function is primarily associated with the response of the density function of a system to a change in number of electrons (N) under the constraint of a constant external potential [v(r)]. To probe the more global reactivity, indicators in the grand canonical ensemble are often obtained by replacing derivatives with respect to N, by derivatives with respect to the chemical potential /x. As a consequence, in the grand canonical ensemble, the local softness sir) replaces the Fukui function/(r). Both quantities are thus mutually related and can be written as follows ... 

Once again, due to the discontinuity of the electron density with respect to N, finite difference approximation leads to three types of Fukui function for a system, namely (l)/+(r) for nucleophilic attack measured by the electron density change following addition of an electron, (2)/ (r) for electrophilic attack measured by the electron density change upon removal of an electron, and (3)/°(r) for radical attack approximated as the average of both previous terms. They are defined as follows ... 

Fukui functions and other response properties can also be derived from the one-electron Kohn-Sham orbitals of the unperturbed system [14]. Following Equation 12.9, Fukui functions can be connected and estimated within the molecular orbital picture as well. Under frozen orbital approximation (FOA of Fukui) and neglecting the second-order variations in the electron density, the Fukui function can be approximated as follows [15] ... 

The Fukui function, denoted by fir), is defined as the differential change in electron density due to an infinitesimal change in the number of electrons [1], That is,... 

When a molecule accepts electrons, the electrons tend to go to places where/1 (r) is large because it is at these locations that the molecule is most able to stabilize additional electrons. Therefore a molecule is susceptible to nucleophilic attack at sites where/ "(r) is large. Similarly, a molecule is susceptible to electrophilic attack at sites where f (r) is large, because these are the regions where electron removal destabilizes the molecule the least. In chemical density functional theory (DFT), the Fukui functions are the key regioselectivity indicators for electron-transfer controlled reactions. 

Based on the foregoing discussion, one might suppose that the Fukui function is nothing more than a DFT-inspired restatement of frontier molecular orbital (FMO) theory. This is not quite true. Because DFT is, in principle, exact, the Fukui function includes effects—notably electron correlation and orbital relaxation—that are a priori neglected in an FMO approach. This is most clear when the electron density is expressed in terms of the occupied Kohn-Sham spin-orbitals [16],... 

In most cases, the orbital relaxation contribution is negligible and the Fukui function and the FMO reactivity indicators give the same results. For example, the Fukui functions and the FMO densities both predict that electrophilic attack on propylene occurs on the double bond (Figure 18.1) and that nucleophilic attack on BF3 occurs at the Boron center (Figure 18.2). The rare cases where orbital relaxation effects are nonnegligible are precisely the cases where the Fukui functions should be preferred over the FMO reactivity indicators [19-22], In short, while FMO theory is based on orbitals from an independent electron approximation like Hartree-Fock or Kohn-Sham, the Fukui function is based on the true many-electron density. 

The utility of the Fukui function for predicting chemical reactivity can also be described using the variational principle for the Fukui function [61,62], The Fukui function from the above discussion, /v (r), represents the best way to add an infinitesimal fraction of an electron to a system in the sense that the electron density pv/v(r) I has lower energy than any other N I -electron density... 

This quantity is trivially computed from the Fukui function, / (r) [78-80], and the shape function, and it has a simple interpretation the shape Fukui function measures where the relative abundance of electrons increases or decreases when electrons are added to (or removed from) a system. In our experience, plotting r) often provides a simpler and easier way to interpret picture of chemical reactivity than the Fukui function itself. Perhaps this is because ofr) is the local density approximation (LDA) to the Fukui function [81]. Since the numerator in Equation 19.27, / (r) — olr), is the post-LDA correction to the Fukui function [81], the shape... 

In a second approach of the reactivity, one fragment A is represented by its electronic density and the other, B, by some reactivity probe of A. In the usual approach, which permits to define chemical hardness, softness, Fukui functions, etc., the probe is simply a change in the total number of electrons of A. [5,6,8] More realistic probes are an electrostatic potential cf>, a pseudopotential (as in Equation 24.102), or an electric field E. For instance, let us consider a homogeneous electric field E applied to a fragment A. How does this field modify the intermolecular forces in A Again, the Hellman-Feynman theorem [22,23] tells us that for an instantaneous nuclear configuration, the force on each atom changes by... 

As mentioned in [Section 24.1], and as already demonstrated in Equation 24.39, the Fukui functions as well as the chemical hardness of an isolated system can be properly defined without invoking any change in its electron number. We define a new Fukui function called polarization Fukui function, which very much resembles the original formulation of the Fukui function but with a different physical interpretation. Because of space limitation, only a brief presentation is given here. More details will appear in a forthcoming work [33]. One assumes a potential variation <5wext(r), which induces a deformation of the density 8p(r). A normalized polarization Fukui function is defined by... 

The effect of external field on reactivity descriptors has been of recent interest. Since the basic reactivity descriptors are derivatives of energy and electron density with respect to the number of electrons, the effect of external field on these descriptors can be understood by the perturbative analysis of energy and electron density with respect to number of electrons and external field. Such an analysis has been done by Senet [22] and Fuentealba [23]. Senet discussed perturbation of these quantities with respect to general local external potential. It can be shown that since p(r) = 8E/8vexl, Fukui function can be seen either as a derivative of chemical potential... 

Yang, W., Parr, R. G., and R. Pucci. 1984. Electron density, Kohn-Sham frontier orbitals, and Fukui functions. J. Chem. Phys. 81 2862-2863. 

This quantity can be viewed as a generalization of Fukui s frontier molecular orbital (MO) concept [25] and plays a key role in linking Frontier MO theory and the HSAB principle. It can be interpreted either as the sensitivity of a system s chemical potential to an external perturbation at a particular point r, or as the change of the electron density p(r) at each point r when the total number of electrons is changed. The former definition has recently been implemented to evaluate this function [26,27] but the derivative of the density with respect to the number of electrons remains by far the most widely used definition. 

This chapter will be concerned with computing the three response functions discussed above—the chemical potential, the chemical hardness, and the Fukui function—as reliably as possible for a neutral molecule in the gas phase. This involves the evaluation of the derivative of the energy and electron density with respect to the number of electrons. 

Until now, we have been concerned with the computation of global properties. We now consider the Fukui function for nucleophilic attack (Equation 34.18), which is a local property that requires the calculation of the electron density of the anion, which... 

---