Theoretical investigation of the titanium-nitrogen heterofullerenes evolved from the smallest fullerene

Mustafa M Kadhim; Evan Abdulkareem Mahmood; Vahideh Abbasi; Mohammad Reza Poor Heravi; Sepideh Habibzadeh; Sarvin Mohammadi-Aghdam; Seyed Mohammad Shoaei

doi:10.1016/j.jmgm.2022.108269

Theoretical investigation of the titanium-nitrogen heterofullerenes evolved from the smallest fullerene

J Mol Graph Model. 2022 Dec:117:108269. doi: 10.1016/j.jmgm.2022.108269. Epub 2022 Jul 9.

Authors

Mustafa M Kadhim¹, Evan Abdulkareem Mahmood², Vahideh Abbasi³, Mohammad Reza Poor Heravi⁴, Sepideh Habibzadeh⁵, Sarvin Mohammadi-Aghdam⁴, Seyed Mohammad Shoaei⁶

Affiliations

¹ Medical Laboratory Techniques Department, Al-Farahidi University, Baghdad, Iraq.
² Medical Laboratory Sciences Department, College of Health Sciences, University of Human Development, Sulaymaniyah, Iraq.
³ Department of Chemistry, University of Zanjan, Zanjan, Iran.
⁴ Department of Chemistry, Payame Noor University, P. O. Box: 19395-3697, Tehran, Iran.
⁵ Department of Chemistry, Payame Noor University, P. O. Box: 19395-3697, Tehran, Iran. Electronic address: sepidehhabibzadeh401@gmail.com.
⁶ Department of Chemistry, Islamic Azad University, Zanjan Branch, Zanjan, Iran.

PMID: 35981466
DOI: 10.1016/j.jmgm.2022.108269

Abstract

In this survey, we are performed kinetic stability, global reactivity, atomic polar tensor (APT) charge and counter plots of Ti-N heterofullerenes developed from C₂₀ fullerene with the molecular formula of C_20-2nTi_nN_n (n = 1-8), at B3PW91/6-311+G∗ level of theory. Also, we are investigated substituent effect of titanium and nitrogen heteroatoms on deuterium adsorption of the heterofullerenes according to density functional theory (DFT). Substituting of Ti-N units with various topology in the cap or equatorial position of heterofullerenes, changes significantly their electronic properties and causes different frontier molecular orbital energy separation (ΔE_HOMO-_LUMO). Hence, C₁₈Ti₁N₁ and C₁₀Ti₅N₅ are found as the best insulated species, while C₁₂Ti₄N₄ and C₄Ti₈N₈ are considered as the strongest conductive nanocage. Also, C₁₄Ti₃N₃ cage shows the highest positive APT charge on Ti atom (+1.357, +1.053), while C₁₂Ti₄N₄ cage shows the lowest positive APT charge on Ti atom (+0.031, -0.292). Accordingly, C₁₄Ti₃N₃, and C₁₂Ti₄N₄ exhibit the lowest, and the highest global electrophilicity; ω of 2.58, and 7.01 eV, respectively. As six D₂ molecules are approached the C₁₄Ti₃N₃ heterofullerene, its ΔE_HOMO-_LUMO (E_g) is increased from 1.29 eV in C₁₄Ti₃N₃ heterofullerene to 2.11 eV in D₂/C₁₄Ti₃N₃ complex (∼+63.57%) indicating high sensitivity of it to adsorption of six D₂ molecules through an exothermic process. As sixteen D₂ molecules approaches the C₄Ti₈N₈ nanocage, its E_g reduces from 0.97 to 0.73 eV (∼-24.74%) indicating high electrical conductivity of D₂/C₄Ti₈N₈ complex. Therefore, C₄Ti₈N₈ as hopeful sensor, can be generate electrical signals when the D₂ molecules approach.

Keywords: APT; Deuterium adsorption; Heterofullerene; Kinetic stability; ΔE(HOMO)-(LUMO).