Second-Order Nonlinear Optical Susceptibilities of Metal-Organic Frameworks Using a Combined Local Field Theory/Charge Embedding Electrostatic Scheme

Tomasz Seidler, Benoît Champagne

Research output: Contribution to journalArticlepeer-review

Abstract

The linear (χ(1)) and second-order nonlinear (χ(2)) optical properties of metal-organic frameworks (MOFs) have been evaluated and interpreted by employing the combined local field theory/charge embedding approach. Three MOFs have been selected, the isostructural bis{4-[2-(4-pyridyl)ethenyl]benzoato}-zinc(II) (PEB-Zn) and bis{4-[2-(4-pyridyl)ethenyl]benzoato}-cadmium(II) (PEB-Cd) and bis{4-[3-(4-pyridyl)ethenyl]benzoato}-cadmium(II) (PEB′-Cd). The simulations, employing the Møller-Plesset second-order perturbation theory level to describe the ion properties, conclude that (i) χ(2) of PEB-Zn (∼60 pm/V at 1064 nm) is about 10% larger than that of PEB-Cd, (ii) χ(2) of PEB′-Cd attains 100 pm/V at 1064 nm [i.e., twice more than that of PEB-Cd or an amplitude similar to that of the 4-(N,N-dimethylamino)-3-acetamidonitrobenzene (DAN) molecular crystal] and (iii) the change of crystal structure accompanying an increase of temperature from 173 to 298 K leads to a decrease of χ(2) by ca. 10%. For the isostructural PEB-Zn and PEB-Cd, the outcome of Kurtz-Perry SHG powder method has been simulated as a function of the grain size, demonstrating that differences between the two MOFs only show up for room temperature structures. A value of 1.29 was estimated for the PEB-Zn/PEB-Cd contrast ratio, in qualitative agreement with experiment (1.16). This work opens the way toward a theoretically based design of MOFs with outstanding second-order nonlinear optical responses. (Graph Presented).

Original languageEnglish
Pages (from-to)6741-6749
Number of pages9
JournalJournal of Physical Chemistry C: Nanomaterials and interfaces
Volume120
Issue number12
DOIs
Publication statusPublished - 31 Mar 2016

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  • PAI n°P7/05 - FS2: Functional Supramolecular Systems (FS2)

    CHAMPAGNE, B. (CoI), De Vos, D. (PI), Van der Auweraer, M. (CoI), Jérôme, C. (CoI), Lazzaroni, R. (CoI), Marin, G. (CoI), Jonas, A. (CoI), Du Prez, F. (CoI), Vanderzande, D. (CoI), Van Tendeloo, G. (CoI), Van Speybroeck, V. (CoI), NENON, S. (Researcher) & STAELENS, N. (Researcher)

    1/04/1230/09/17

    Project: Research

  • consortium des équipements de calcul intensif

    Champagne, B. (CoI)

    1/01/1131/12/22

    Project: Research

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