TY - JOUR UR - http://lib.ugent.be/catalog/pug01:2041511 ID - pug01:2041511 LA - eng TI - Influence of electron correlation and degeneracy on the Fukui matrix and extension of frontier molecular orbital theory to correlated quantum chemical methods PY - 2012 JO - (2012) PHYSICAL CHEMISTRY CHEMICAL PHYSICS SN - 1463-9076 PB - 2012 AU - Bultinck, Patrick WE06 801000931055 0000-0003-2766-2672 AU - Van Neck, Dimitri WE05 801000661071 0000-0001-9687-1895 AU - Acke, Guillaume WE06 002005608776 AU - Ayers, Paul W AB - The Fukui function is considered as the diagonal element of the Fukui matrix in position space, where the Fukui matrix is the derivative of the one particle density matrix (1DM) with respect to the number of electrons. Diagonalization of the Fukui matrix, expressed in an orthogonal orbital basis, explains why regions in space with negative Fukui functions exist. Using a test set of molecules, electron correlation is found to have a remarkable effect on the eigenvalues of the Fukui matrix. The Fukui matrices at the independent electron model level are mathematically proven to always have an eigenvalue equal to exactly unity while the rest of the eigenvalues possibly differ from zero but sum to zero. The loss of idempotency of the 1DM at correlated levels of theory causes the loss of these properties. The influence of electron correlation is examined in detail and the frontier molecular orbital concept is extended to correlated levels of theory by defining it as the eigenvector of the Fukui matrix with the largest eigenvalue. The effect of degeneracy on the Fukui matrix is examined in detail, revealing that this is another way by which the unity eigenvalue and perfect pairing of eigenvalues can disappear. ER -Download RIS file
00000nam^a2200301^i^4500 | |||
001 | 2041511 | ||
005 | 20180813141346.0 | ||
008 | 120223s2012------------------------eng-- | ||
022 | a 1463-9076 | ||
024 | a 000299505400036 2 wos | ||
024 | a 1854/LU-2041511 2 handle | ||
024 | a 10.1039/c2cp22543c 2 doi | ||
040 | a UGent | ||
245 | a Influence of electron correlation and degeneracy on the Fukui matrix and extension of frontier molecular orbital theory to correlated quantum chemical methods | ||
260 | c 2012 | ||
520 | a The Fukui function is considered as the diagonal element of the Fukui matrix in position space, where the Fukui matrix is the derivative of the one particle density matrix (1DM) with respect to the number of electrons. Diagonalization of the Fukui matrix, expressed in an orthogonal orbital basis, explains why regions in space with negative Fukui functions exist. Using a test set of molecules, electron correlation is found to have a remarkable effect on the eigenvalues of the Fukui matrix. The Fukui matrices at the independent electron model level are mathematically proven to always have an eigenvalue equal to exactly unity while the rest of the eigenvalues possibly differ from zero but sum to zero. The loss of idempotency of the 1DM at correlated levels of theory causes the loss of these properties. The influence of electron correlation is examined in detail and the frontier molecular orbital concept is extended to correlated levels of theory by defining it as the eigenvector of the Fukui matrix with the largest eigenvalue. The effect of degeneracy on the Fukui matrix is examined in detail, revealing that this is another way by which the unity eigenvalue and perfect pairing of eigenvalues can disappear. | ||
598 | a A1 | ||
100 | a Bultinck, Patrick u WE06 0 801000931055 0 0000-0003-2766-2672 | ||
700 | a Van Neck, Dimitri u WE05 0 801000661071 0 0000-0001-9687-1895 | ||
700 | a Acke, Guillaume u WE06 0 002005608776 0 802000450781 | ||
700 | a Ayers, Paul W | ||
650 | a Physics and Astronomy | ||
653 | a REACTIVITY | ||
653 | a SIMILARITY | ||
653 | a ENERGY | ||
653 | a NUMBER | ||
653 | a ATOMS | ||
653 | a NON-NEGATIVITY | ||
653 | a FUNCTION INDEXES | ||
653 | a KOOPMANS THEOREM | ||
653 | a DENSITY-FUNCTIONAL THEORY | ||
773 | t PHYSICAL CHEMISTRY CHEMICAL PHYSICS g Phys. Chem. Chem. Phys. 2012. 14 (7) p.2408-2416 q 14:7<2408 | ||
856 | 3 Full Text u https://biblio.ugent.be/publication/2041511/file/2041530 z [ugent] y fukui.pdf | ||
920 | a article | ||
Z30 | x WE 1 WE05 | ||
922 | a UGENT-WE | ||
Z30 | x WE 1 WE06 | ||
922 | a UGENT-WE | ||
Z30 | x WE 1 WE06* | ||
922 | a UGENT-WE |
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