TY - JOUR
T1 - Efficient computation of density-functional orbitally resolved reactivity indices
AU - Mineva, Tzonka
AU - Heine, Thomas
N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2004/12/16
Y1 - 2004/12/16
N2 - An algorithm for computation of density-functional-based orbital reactivity indices, such as orbitally resolved hardness and softness tensors, total hardness and softness, and the Fukui indices, has been extended for systems with degenerate electronic states and implemented in the deMon computer code. The method treats explicitly degenerate orbitals, thus avoiding spurious numerical errors in hardness tensor computations. Benchmark calculations for a series of small molecules and some larger, highly degenerate systems reveal good computational performance and numerical stability. The influence of the choice of auxiliary basis functions on the results is also examined and discussed. The predicted orbital and total reactivity index values are found to be insensitive to the applied exchange-correlation functionals. Applications of the orbital Fukui indices to a series of (4n + 2) π-electron [n]-annulenes show the possibility of rationalizing the reactivity of individual molecular orbital contributions.
AB - An algorithm for computation of density-functional-based orbital reactivity indices, such as orbitally resolved hardness and softness tensors, total hardness and softness, and the Fukui indices, has been extended for systems with degenerate electronic states and implemented in the deMon computer code. The method treats explicitly degenerate orbitals, thus avoiding spurious numerical errors in hardness tensor computations. Benchmark calculations for a series of small molecules and some larger, highly degenerate systems reveal good computational performance and numerical stability. The influence of the choice of auxiliary basis functions on the results is also examined and discussed. The predicted orbital and total reactivity index values are found to be insensitive to the applied exchange-correlation functionals. Applications of the orbital Fukui indices to a series of (4n + 2) π-electron [n]-annulenes show the possibility of rationalizing the reactivity of individual molecular orbital contributions.
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U2 - 10.1021/jp048000z
DO - 10.1021/jp048000z
M3 - Article
AN - SCOPUS:10944227484
VL - 108
SP - 11086
EP - 11091
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 50
ER -