Performance of multi-configurational calculations for a 1,4-bis(phenylethynyl)benzene derivative conjugated molecule.
The theoretical challenge of finding a single method that quantitatively reproduces both the experimental low-lying excitation energies and the torsional barrier of a prototypical conjugated molecule, which could act as a molecular wire, has been addressed here. The results indicate that this goal can be reasonably achieved when multi-reference perturbation theory up to second order (MRMP2) based on a complete active space self-consistent field (CASSCF) wave function using large active spaces is used. The results obtained were also used to compare with less expensive Kohn-Sham (KS) density functional theory (DFT) calculations when applied to these properties. The results obtained with BLYP and B3LYP exchange-correlation functionals indicate that quantitative agreement with all the experimental data cannot be obtained with this methodology, with a clear dependence on the exchange-correlation form selected. We thus encourage a careful testing of pure and hybrid density functionals whenever KS DFT is used for the rational design of conjugated materials for charge conduits.
Sancho-García
J C
JC
Departamento de Química Física, Universidad de Alicante, Alicante, Spain. JC.Sancho@ua.es
Pérez-Jiménez
A J
AJ
D000480:Alkynes / Q000737:chemistry*; D000840:Anisoles / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D003198:Computer Simulation; D008956:Models, Chemical; D015394:Molecular Structure; D011789:Quantum Theory
C529779:1,4-bis(4-methoxyphenylethynyl)benzene; D000480:Alkynes; D000840:Anisoles; D001555:Benzene Derivatives