Theoretical insight into the second-order NLO response of the bis{4-[2-(4-pyridyl)ethenyl]benzoato}-zinc(II) metal-organic framework

Yuexing Zhang, Benoît Champagne*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

20 Scopus citations

Abstract

Ab initio wavefunction and density functional theory calculations have been performed to investigate the second-order nonlinear optical (NLO) properties of the bis{4-[2-(4-pyridyl)ethenyl]benzoato}-zinc(II) metal-organic framework (MOF). This has been carried out by adopting the supramolecular or cluster approach, which consists in analyzing the evolution of the first hyperpolarizability as a function of the number of units of the system. In a first step, the impact of the method of calculation has been assessed, evidencing that the exchange-correlation functional has a stronger impact on the first hyperpolarizability (β) values than the basis set. Still, the first hyperpolarizability values related to the hyper-Rayleigh scattering (HRS) (β HRS) are slightly more sensitive to the Zn basis set than to that of the other atoms, but the combination of the LANL2DZ basis for Zn with the 6-31G* basis set for the other atoms provides stable results with respect to adding supplementary valence, polarization, and diffuse functions as demonstrated by the variations of β HRS that remain smaller than 6%. Several structure/property relationships have then been deduced for the β of this MOF: (i) the lack of coordination of the ligands extremities enhances β because their donor/acceptor characters are not damped by the Zn 2+ cations, (ii) the β of clusters expanding in one direction increases almost linearly with the cluster size, (iii) the deviations with respect to linearity are smaller than 25%, which differ from organic molecular crystals, and (iv) the octupolar component of the β response is of the same order of magnitude as its dipolar counterpart, and its relative importance generally increases with the cluster size.

Original languageEnglish (US)
Pages (from-to)21973-21981
Number of pages9
JournalJournal of Physical Chemistry C
Volume116
Issue number41
DOIs
StatePublished - Oct 18 2012

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films

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