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Understanding structure-activity relation in VxOy clusters of varied stoichiometry and sizes through conceptual density functional approach.
J Mol Model 2019; 25(11):319JM

Abstract

Computations have been performed on VxOy clusters (with x = 1-8, y = 1-21) to explore their structure, stability, and reactivity based on local and global reactivity descriptors defined within the formalism of density functional theory (DFT). The vertical and adiabatic ionization energies and electron affinities are in accordance with Franck-Condon principle and suggest that the VxOy clusters are more likely to be electron acceptors than donors. The structure and reactivity of VxOy clusters delicately depend on their oxygen content and environment. Distinct active sites have been identified for each cluster species on the basis of coordination, symmetry, and charge distribution. The propensity of all the reactive sites towards an approaching electrophile and/or nucleophile has been studied using local reactivity descriptor. In oxygen-poor clusters, the vanadium atoms are more prone to nucleophilic attack. With an increase in oxygen concentration, the coordination number of vanadium increases and reaches four-fold, the site for nucleophilic attack shifts to terminal oxygens. We conclude that of all the stoichiometries, the stable VxOy clusters have the (VO3)a(V2O5)b formula unit. The localization of positive charge density in cubic cage structure of V8O20 successfully traps halide ions (F-, Cl-, and Br-). In view of increasing use of metal oxide clusters in heterogeneous catalysis, the understanding of structure-activity relationship in vanadium oxides' clusters provided in the current study is highly desirable.

Authors+Show Affiliations

Theoretical & Computational Chemistry Group, Department of Chemistry & Centre for Advanced Studies in Chemistry, Panjab University, Chandigarh, 160014, India.University Institute of Engineering and Technology, Panjab University, Chandigarh, 160014, India. Sgupta@pu.ac.in.Theoretical & Computational Chemistry Group, Department of Chemistry & Centre for Advanced Studies in Chemistry, Panjab University, Chandigarh, 160014, India. neetugoel@pu.ac.in.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31598882

Citation

Kaur, Navjot, et al. "Understanding Structure-activity Relation in VxOy Clusters of Varied Stoichiometry and Sizes Through Conceptual Density Functional Approach." Journal of Molecular Modeling, vol. 25, no. 11, 2019, p. 319.
Kaur N, Gupta S, Goel N. Understanding structure-activity relation in VxOy clusters of varied stoichiometry and sizes through conceptual density functional approach. J Mol Model. 2019;25(11):319.
Kaur, N., Gupta, S., & Goel, N. (2019). Understanding structure-activity relation in VxOy clusters of varied stoichiometry and sizes through conceptual density functional approach. Journal of Molecular Modeling, 25(11), p. 319. doi:10.1007/s00894-019-4168-3.
Kaur N, Gupta S, Goel N. Understanding Structure-activity Relation in VxOy Clusters of Varied Stoichiometry and Sizes Through Conceptual Density Functional Approach. J Mol Model. 2019 Oct 9;25(11):319. PubMed PMID: 31598882.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Understanding structure-activity relation in VxOy clusters of varied stoichiometry and sizes through conceptual density functional approach. AU - Kaur,Navjot, AU - Gupta,Shuchi, AU - Goel,Neetu, Y1 - 2019/10/09/ PY - 2019/04/04/received PY - 2019/08/15/accepted PY - 2019/10/11/entrez PY - 2019/10/11/pubmed PY - 2019/10/11/medline KW - Density functional theory KW - Global reactivity descriptors KW - Local reactivity descriptors KW - VxOy clusters SP - 319 EP - 319 JF - Journal of molecular modeling JO - J Mol Model VL - 25 IS - 11 N2 - Computations have been performed on VxOy clusters (with x = 1-8, y = 1-21) to explore their structure, stability, and reactivity based on local and global reactivity descriptors defined within the formalism of density functional theory (DFT). The vertical and adiabatic ionization energies and electron affinities are in accordance with Franck-Condon principle and suggest that the VxOy clusters are more likely to be electron acceptors than donors. The structure and reactivity of VxOy clusters delicately depend on their oxygen content and environment. Distinct active sites have been identified for each cluster species on the basis of coordination, symmetry, and charge distribution. The propensity of all the reactive sites towards an approaching electrophile and/or nucleophile has been studied using local reactivity descriptor. In oxygen-poor clusters, the vanadium atoms are more prone to nucleophilic attack. With an increase in oxygen concentration, the coordination number of vanadium increases and reaches four-fold, the site for nucleophilic attack shifts to terminal oxygens. We conclude that of all the stoichiometries, the stable VxOy clusters have the (VO3)a(V2O5)b formula unit. The localization of positive charge density in cubic cage structure of V8O20 successfully traps halide ions (F-, Cl-, and Br-). In view of increasing use of metal oxide clusters in heterogeneous catalysis, the understanding of structure-activity relationship in vanadium oxides' clusters provided in the current study is highly desirable. SN - 0948-5023 UR - https://www.unboundmedicine.com/medline/citation/31598882/Understanding_structure-activity_relation_in_VxOy_clusters_of_varied_stoichiometry_and_sizes_through_conceptual_density_functional_approach L2 - https://dx.doi.org/10.1007/s00894-019-4168-3 DB - PRIME DP - Unbound Medicine ER -