Generalization of the Kohn–Sham equations with constrained electron density formalism and its time‐dependent response theory formulation

The Kohn-Sham equations with constrained electron density (KSCED) embedding formalism of Wesoowski and coworkers was originally developed and is good for the case of two weakly interacting molecular regions with weakly overlapping densities, such as might be expected in describing solvation. A generalization is given here for the case of three molecular regions with strongly overlapping densities with the idea that this generalized theory can offer a better description of embedding in the context of situations that might be encountered in, for example, chemisorption on surfaces or active sites in enzymes. This three-partition generalization includes the original two-partition formalism as a special case. Time-dependent response theory equations are then developed for the two- and three-partition theories for application to the problem of the calculation of polarizabilities and other response properties, including excitation spectra, of embedded molecules or molecular structures.

[1]  K. Morokuma,et al.  A NEW ONIOM IMPLEMENTATION IN GAUSSIAN98. PART I. THE CALCULATION OF ENERGIES, GRADIENTS, VIBRATIONAL FREQUENCIES AND ELECTRIC FIELD DERIVATIVES , 1999 .

[2]  Mark E. Casida,et al.  Time-Dependent Density Functional Response Theory of Molecular Systems: Theory, Computational Methods, and Functionals , 1996 .

[3]  L. D. Künne,et al.  Recent Developments and Applications of Modern Density Functional Theory , 1998 .

[4]  L. H. Thomas.  The calculation of atomic fields , 1927, Mathematical Proceedings of the Cambridge Philosophical Society.

[5]  N. Govind,et al.  Prediction of electronic excited states of adsorbates on metal surfaces from first principles. , 2001, Physical review letters.

[6]  T. Wesołowski.  Density Functional Theory with approximate kinetic energy functionals applied to hydrogen bonds , 1997 .

[7]  L. Reining,et al.  Electronic excitations: density-functional versus many-body Green's-function approaches , 2002 .

[8]  Robert van Leeuwen,et al.  KEY CONCEPTS IN TIME-DEPENDENT DENSITY-FUNCTIONAL THEORY , 2001 .

[9]  M. E. Casida.  Jacob's Ladder for Time-Dependent Density-Functional Theory: Some Rungs on the Way to Photochemical Heaven , 2002 .

[10]  K. Morokuma,et al.  On the application of the IMOMO (integrated molecular orbital + molecular orbital) method , 2000 .

[11]  Mark Earl Casida,et al.  In Recent Advances in Density-Functional Methods , 1995 .

[12]  A. Warshel,et al.  Frozen density functional approach for ab initio calculations of solvated molecules , 1993 .

[13]  Tomasz A Wesołowski.  Comment on "Prediction of electronic excited states of adsorbates on metal surfaces from first principles". , 2002, Physical review letters.

[14]  Jacques Weber,et al.  Kohn-Sham equations with constrained electron density: an iterative evaluation of the ground-state electron density of interacting molecules , 1996 .

[15]  Jorge M. Seminario,et al.  Recent developments and applications of modern density functional theory , 1996 .

[16]  Vincenzo Barone,et al.  Recent Advances in Density Functional Methods Part III , 2002 .

[17]  Cortona,et al.  Self-consistently determined properties of solids without band-structure calculations. , 1991, Physical review. B, Condensed matter.

[18]  T. Wesołowski,et al.  Gradient-free and gradient-dependent approximations in the total energy bifunctional for weakly overlapping electron densities , 2003 .

[19]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[20]  Tomasz A. Wesol owski.  Comment on “Anisotropic intermolecular interactions in van der Waals and hydrogen-bonded complexes: What can we get from density-functional calculations?” [J. Chem. Phys. 111, 7727 (1999)] , 2000 .

[21]  N. Govind,et al.  Electronic-structure calculations by first-principles density-based embedding of explicitly correlated systems , 1999 .

[22]  Deborah G Evans.  Theoretical Methods in Condensed Phase Chemistry. Progress in Theoretical Chemistry and Physics. Volume 5 Edited by Steven D. Schwartz (Albert Einstein College of Medicine). Kluwer Academic: Dordrecht, Boston, London. 2000. xii + 304 pp. $125.00. ISBN: 0-7923-6697-5. , 2001 .

[23]  T. Wesołowski,et al.  Intermolecular interaction energies from the total energy bifunctional: A case study of carbazole complexes , 2002 .

[24]  E. Fermi.  Eine statistische Methode zur Bestimmung einiger Eigenschaften des Atoms und ihre Anwendung auf die Theorie des periodischen Systems der Elemente , 1928 .

[25]  T. Wesołowski,et al.  Properties of CO adsorbed in ZSM5 zeolite: Density functional theory study using the embedding scheme based on electron density partitioning , 2001 .

[26]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .