DFT investigation of the influence of Jahn-Teller distortion on the aromaticity in square-planar arsenic and antimony clusters
Abstract
Density functional theory (DFT) calculations were performed to investigate aromaticity of tetra atomic metalloid clusters, As-4(2-) and Sb-4(2-). The careful analysis of nuclear independent chemical shifts (NICS) revealed strong sigma antiaromatic and week pi aromatic character of investigated species. This unexpected behavior is explained through the analysis of antagonistic paratropic and diatropic contributions, and with detailed adaptive natural density partitioning (AdNDP) analysis. Furthermore, we investigated aromatic/antiaromatic behavior of Jahn-Teller (JT) active species As-4(-) and Sb-4(-). NICS parameters have been scanned along the Intrinsic Distortion Path (IDP) showing strong antiaromaticity which decreases with increasing deviation from D-4h to D-2h symmetry.
Keywords:
DFT / Metalloid clusters / Aromaticity / Jahn-TellerSource:
Polyhedron, 2014, 80, 69-80Publisher:
- Oxford : Pergamon-Elsevier Science Ltd
Funding / projects:
- Rational design and synthesis of biologically active and coordination compounds and functional materials, relevant for (bio)nanotechnology (RS-172035)
- Swiss National Science Foundation
DOI: 10.1016/j.poly.2014.02.005
ISSN: 0277-5387
WoS: 000341348300010
Scopus: 2-s2.0-84905486047
Collections
Institution/Community
IHTMTY - JOUR AU - Perić, Marko AU - Anđelković, Ljubica AU - Zlatar, Matija AU - Daul, Claude AU - Gruden-Pavlović, Maja PY - 2014 UR - https://cer.ihtm.bg.ac.rs/handle/123456789/1427 AB - Density functional theory (DFT) calculations were performed to investigate aromaticity of tetra atomic metalloid clusters, As-4(2-) and Sb-4(2-). The careful analysis of nuclear independent chemical shifts (NICS) revealed strong sigma antiaromatic and week pi aromatic character of investigated species. This unexpected behavior is explained through the analysis of antagonistic paratropic and diatropic contributions, and with detailed adaptive natural density partitioning (AdNDP) analysis. Furthermore, we investigated aromatic/antiaromatic behavior of Jahn-Teller (JT) active species As-4(-) and Sb-4(-). NICS parameters have been scanned along the Intrinsic Distortion Path (IDP) showing strong antiaromaticity which decreases with increasing deviation from D-4h to D-2h symmetry. PB - Oxford : Pergamon-Elsevier Science Ltd T2 - Polyhedron T1 - DFT investigation of the influence of Jahn-Teller distortion on the aromaticity in square-planar arsenic and antimony clusters VL - 80 SP - 69 EP - 80 DO - 10.1016/j.poly.2014.02.005 ER -
@article{ author = "Perić, Marko and Anđelković, Ljubica and Zlatar, Matija and Daul, Claude and Gruden-Pavlović, Maja", year = "2014", abstract = "Density functional theory (DFT) calculations were performed to investigate aromaticity of tetra atomic metalloid clusters, As-4(2-) and Sb-4(2-). The careful analysis of nuclear independent chemical shifts (NICS) revealed strong sigma antiaromatic and week pi aromatic character of investigated species. This unexpected behavior is explained through the analysis of antagonistic paratropic and diatropic contributions, and with detailed adaptive natural density partitioning (AdNDP) analysis. Furthermore, we investigated aromatic/antiaromatic behavior of Jahn-Teller (JT) active species As-4(-) and Sb-4(-). NICS parameters have been scanned along the Intrinsic Distortion Path (IDP) showing strong antiaromaticity which decreases with increasing deviation from D-4h to D-2h symmetry.", publisher = "Oxford : Pergamon-Elsevier Science Ltd", journal = "Polyhedron", title = "DFT investigation of the influence of Jahn-Teller distortion on the aromaticity in square-planar arsenic and antimony clusters", volume = "80", pages = "69-80", doi = "10.1016/j.poly.2014.02.005" }
Perić, M., Anđelković, L., Zlatar, M., Daul, C.,& Gruden-Pavlović, M.. (2014). DFT investigation of the influence of Jahn-Teller distortion on the aromaticity in square-planar arsenic and antimony clusters. in Polyhedron Oxford : Pergamon-Elsevier Science Ltd., 80, 69-80. https://doi.org/10.1016/j.poly.2014.02.005
Perić M, Anđelković L, Zlatar M, Daul C, Gruden-Pavlović M. DFT investigation of the influence of Jahn-Teller distortion on the aromaticity in square-planar arsenic and antimony clusters. in Polyhedron. 2014;80:69-80. doi:10.1016/j.poly.2014.02.005 .
Perić, Marko, Anđelković, Ljubica, Zlatar, Matija, Daul, Claude, Gruden-Pavlović, Maja, "DFT investigation of the influence of Jahn-Teller distortion on the aromaticity in square-planar arsenic and antimony clusters" in Polyhedron, 80 (2014):69-80, https://doi.org/10.1016/j.poly.2014.02.005 . .