Lithuanian Journal of Physics article / Lietuvos fizikos žurnalo straipsnis

MODEL FOR SELF-ASSEMBLY OF Br–H AND Br–Br BONDED Br₄Py MOLECULES
Andrius Ibenskas^a, Evaldas E. Tornau^a, and Mantas Šimėnas^b
^aCenter for Physical Sciences and Technology, Saulėtekio 3, 10257 Vilnius, Lithuania
^bFaculty of Physics, Vilnius University, Saulėtekio 9, 10222 Vilnius, Lithuania
Email: andrius.ibenskas@ftmc.lt

Received 12 September 2022; accepted 3 October 2022

A model, based on the pairwise intermolecular halogen–hydrogen (Br–H) and halogen–halogen (Br–Br) bonding, is proposed to describe the self-assembly of Br₄Py molecules into two different planar structures (Phase I and Phase II). The pair bonding interactions are calculated by the density functional theory for the two-molecule and four-molecule clusters. It is shown that about 60% of bonding strength is due to the electrostatic Br(top)–Br(belt) interactions, while the remaining originates from Br–H interactions. The obtained values of pair interactions are further used for Monte Carlo calculations. The model for these calculations is proposed on a square lattice. The two main pair interactions are needed for the emergence of the Phase I ordering, while the Phase II ordering is obtained using a single interaction. The obtained results explain the emergence of both phases.
Keywords: molecular self-assembly, statistical models of phase transitions, Monte Carlo simulations, density functional theory calculations

Br–H IR Br–Br RYŠIAIS SUSIJUNGIANČIŲ Br₄Py MOLEKULIŲ SAVAIMINIO SUSITVARKYMO MODELIS
Andrius Ibenskas^a, Evaldas E. Tornau^a, Mantas Šimėnas^b

^aFizinių ir technologijos mokslų centras, Vilnius, Lietuva
^bVilniaus universiteto Fizikos fakultetas, Vilnius, Lietuva

1,3,6,8-tetrabromopireno (Br₄Py) molekulių susitvarkymui į dvi skirtingas plokščias struktūras (I ir II fazes) aprašyti yra siūlomas gardelės modelis, grindžiamas porinėmis tarpmolekulinėmis halogeno–vandenilio (Br–H) ir halogeno–halogeno (Br–Br) sąveikomis ant kvadratinės gardelės. Porinių sąveikų energijos įvertinamos skaičiuojant tankio funkcionalą dviejų molekulių ir keturių molekulių klasteriams. Rezultatai rodo, kad apie 60 % sąveikų energijos sudaro elektrostatiniai Br (viršus) – Br (šonas) ryšiai, o likusi dalis atsiranda dėl Br–H ryšių. Gautos sąveikų energijų vertės toliau naudojamos Monte Karlo skaičiavimams atlikti, remiantis pasiūlytu gardelės modeliu. I fazei susiformuoti reikalingos dvi pagrindinės porinės sąveikos, o išsidėstyti į II fazę užtenka vieno sąveikos tipo. Gauti rezultatai paaiškina abiejų fazių susidarymo ypatumus.

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