ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Frequency-dependent optical response and selective adsorptive properties of MOF-199: insight from the DFT, Monte Carlo and molecular dynamics simulations

Nathanael Damilare Ojo, Margaret Damilola Olawale, Blessing Bukola Olalere, Olayinka Azeez Ladigbolu, and Oluwatoba Emmanuel Oyeneyin

Department of Chemistry, University of Ibadan, Ibadan, Nigeria

E-mail: dammynath@yahoo.com

Received: 25 June 2025  Accepted: 24 December 2025

Abstract:

Understanding the molecular and optical properties of metal–organic frameworks (MOF) gives insight into their applications. Here, we studied the molecular, optical, electronic and adsorption properties of MOF-199 using density functional theory (DFT), Monte Carlo (MC) and molecular dynamics (MD) methods. The dynamic nonlinear optical (NLO) properties (electrooptic Pockels effect: [β(− ω;ω,0)]; dynamic first hyperpolarizability: β(− 2ω;ω,ω)]; electrooptic Kerr effect: γ(− ω;ω,0,0)]; and the direct current second harmonic generation: [γ(− 2ω;ω,ω,0)]) were studied at two laser frequencies (ħω = 0.085645 au; ħω = 0.042823 au). The kinetic reactivity of the MOF was revealed by its low energy gap, depicting its semiconducting potential. The nucleophilic sites were the carboxylic acid oxygen with a negative electrostatic potential. The MC and MD revealed that MOF-199 displayed good adsorption properties towards CH₄, CO₂, NH₃ and H₂S molecules. The adsorption capacity was confirmed to be via physical and/or chemical interactions as depicted by the close contact and pair distribution function analyses. However, MOF-199 portrayed strong binding affinity for H₂S (r = 2.7–5.0 Å) and CO₂ (r = 3.2–4.6 Å) gases. Additionally, except β(− 2ω;ω,ω), other studied dynamic NLO properties viz EOKE, EOPE, and DCSHG of the MOF were enhanced under high-energy laser frequency (λ = 532 nm; ħω = 0.085645 au) by approximately two, five, and twenty-two times, respectively, indicating good potential applications in optical communication, laser technology, rapatronic photography, and carrier dynamics.

Keywords: MOF-199; Dynamic NLO; Global warming; Pair distribution function; DFT

Full paper is available at www.springerlink.com.

DOI: 10.1007/s11696-025-04621-4

Chemical Papers 80 (4) 3387–3405 (2026)