Document Server@UHasselt >
Research publications >
Please use this identifier to cite or link to this item:
|Title: ||A benchmark theoretical study of the electron affinities of benzene and linear acenes|
|Authors: ||HAJGATO, Balazs|
De Proft, F.
|Issue Date: ||2008|
|Publisher: ||AMER INST PHYSICS|
|Citation: ||JOURNAL OF CHEMICAL PHYSICS, 129(8)|
|Abstract: ||A benchmark theoretical determination of the electron affinities of benzene and linear oligoacenes ranging from naphthalene to hexacene is presented, using the principles of a focal point analysis. These energy differences have been obtained from a series of single-point calculations at the Hartree-Fock, second-, third-, and partial fourth-order Moller-Plesset (MP2, MP3, and MP4SDQ) levels and from coupled cluster calculations including single and double excitations (CCSD) as well as perturbative estimates of connected triple excitations [CCSD(T)], using basis sets of improving quality, containing up to 1386, 1350, 1824, 1992, 1630, and 1910 basis functions in the computations, respectively. Studies of the convergence properties of these energy differences as a function of the size of the basis set and order attained in electronic correlation enable a determination of the vertical electron affinities of the four larger terms of the oligoacene (C2+4nH2+2n) series within chemical accuracy (0.04 eV). According to our best estimates, these amount to +0.28, +0.82, +1.21, and +1.47 eV when n = 3, 4, 5, and 6. Adiabatic electron affinities have been further calculated by incorporating corrections for zero-point vibrational energies and for geometrical relaxations. The same procedure was applied to determine the vertical electron affinities of benzene and naphthalene, which are found to be markedly negative (similar to-1.53 and similar to-0.48 eV, respectively). Highly quantitative insights into experiments employing electron transmission spectroscopy on these compounds were also amenable from such an approach, provided diffuse atomic functions are deliberately removed from the basis set, in order to enforce confinement in the molecular region and enable a determination of pseudoadiabatic electron affinities (with respect to the timescale of nuclear motions). Comparison was made with calculations employing density functional theory and especially designed models that exploit the integer discontinuity in the potential or incorporate a potential wall in the unrestricted Kohn-Sham orbital equation for the anion. (c) 2008 American Institute of Physics.|
|Notes: ||Hasselt Univ, Dept SBG, Res Grp Theoret Chem, B-3590 Diepenbeek, Belgium. Univ Durham, Dept Chem, Durham DH1 3LE, England. Vrije Univ Brussels, B-1050 Brussels, Belgium.|
|ISI #: ||000259008900016|
|Type: ||Journal Contribution|
|Validation: ||ecoom, 2009|
|Appears in Collections: ||Research publications|
Files in This Item:
There are no files associated with this item.
Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.