ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
A dynamical partitioning of the reaction field is proposed in order to study the electron density flow along the reaction coordinate. The density functional is constructed in a universal form, and a one-to-one correspondence is established between the density matrix and the electron density. The density functional is free from the constraints of N or v representability and is treated as a thermodynamic function that obeys the principle of maximum entropy. The functional derivative of the density functional with respect to the electron density is introduced as a response operator. The reaction paths are combinations of the dynamical processes of the electron density; the corresponding response operators and new type of thermodynamic functions and potentials are defined and shown to be useful. The characteristic features of the chemical reaction coordinate is discussed in terms of the new thermodynamic quantities. The importance of the softest vibrational mode as the chemical reactivity index is rationalized in terms of the density functional theory.
Additional Material:
1 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560320721
