First-principles characterisation of spectroscopic and bonding properties of cationic bismuth carbide clusters

Diogo A.F. Almeida; Micael J.T. Oliveira; Bruce F. Milne

doi:10.48550/arXiv.2102.09869

First-principles characterisation of spectroscopic and bonding properties of cationic bismuth carbide clusters

Diogo A.F. Almeida^* (Corresponding Author), Micael J.T. Oliveira^* (Corresponding Author), Bruce F. Milne^* (Corresponding Author)

^*Corresponding author for this work

Chemistry

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Abstract

Vibrational and electronic absorption spectra calculated at the (time-dependent) density functional theory level for the bismuth carbide clusters BinC2n+ (3⩽n⩽9) indicate significant differences in types of bonding that depend on cluster geometry. Analysis of the electronic charge densities of these clusters highlighted bonding trends in these complex open-shell systems consistent with the spectroscopic information. The data indicate that larger clusters (n>5) have significant non-covalent bonding character and are likely to be kinetically unstable, in agreement with the cluster mass distribution obtained in gas-aggregation source experiments. The spectral fingerprints of the different clusters obtained from our calculations also suggest that identification of specific BinC2n+ structural isomers should be possible based on infra-red and optical absorption spectroscopy.

Original language	English
Article number	113372
Number of pages	1
Journal	Computational and Theoretical Chemistry
Volume	1204
Early online date	30 Jul 2021
DOIs	https://doi.org/10.48550/arXiv.2102.09869 https://doi.org/10.1016/j.comptc.2021.113372
Publication status	Published - 1 Oct 2021

Bibliographical note

Acknowledgements

This work was supported by national funds from the Portuguese Foundation for Science and Technology (FCT) within the projects UIDB/04564/2020, UIDP/04564/2020, PTDC/FIS/103587/2008, SFRH/BPD/44608/2008, CONT-DOUT/11/UC/405/10150/18/2008, POCI-01-0145-FEDER-032229 and CENTRO-01-0145-FEDER-000014, 2017-2020. The authors thank the Laboratory for Advanced Computation of the University of Coimbra for the provision of computer resources, technical support and assistance. BFM acknowledges support from the Donostia International Physics Centre and the Centro de Física de Materiales (UPV/EHU), San Sebastián, Spain.

Data Availability Statement

Supplementary data associated with this article can be found, in the online version, at https://doi.org/10.1016/j.comptc.2021.113372.

Keywords

Bismuth carbide
Clusters
Density functional theory
Relativistic
Spectroscopy
Bonding

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First-principles characterisation of spectroscopic and bonding properties of cationic bismuth carbide clusters. / Almeida, Diogo A.F. (Corresponding Author); Oliveira, Micael J.T. (Corresponding Author); Milne, Bruce F. (Corresponding Author).
In: Computational and Theoretical Chemistry, Vol. 1204, 113372, 01.10.2021.

Research output: Contribution to journal › Article › peer-review

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abstract = "Vibrational and electronic absorption spectra calculated at the (time-dependent) density functional theory level for the bismuth carbide clusters BinC2n+ (3⩽n⩽9) indicate significant differences in types of bonding that depend on cluster geometry. Analysis of the electronic charge densities of these clusters highlighted bonding trends in these complex open-shell systems consistent with the spectroscopic information. The data indicate that larger clusters (n>5) have significant non-covalent bonding character and are likely to be kinetically unstable, in agreement with the cluster mass distribution obtained in gas-aggregation source experiments. The spectral fingerprints of the different clusters obtained from our calculations also suggest that identification of specific BinC2n+ structural isomers should be possible based on infra-red and optical absorption spectroscopy.",

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note = "Acknowledgements This work was supported by national funds from the Portuguese Foundation for Science and Technology (FCT) within the projects UIDB/04564/2020, UIDP/04564/2020, PTDC/FIS/103587/2008, SFRH/BPD/44608/2008, CONT-DOUT/11/UC/405/10150/18/2008, POCI-01-0145-FEDER-032229 and CENTRO-01-0145-FEDER-000014, 2017-2020. The authors thank the Laboratory for Advanced Computation of the University of Coimbra for the provision of computer resources, technical support and assistance. BFM acknowledges support from the Donostia International Physics Centre and the Centro de F{\'i}sica de Materiales (UPV/EHU), San Sebasti{\'a}n, Spain.",

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N2 - Vibrational and electronic absorption spectra calculated at the (time-dependent) density functional theory level for the bismuth carbide clusters BinC2n+ (3⩽n⩽9) indicate significant differences in types of bonding that depend on cluster geometry. Analysis of the electronic charge densities of these clusters highlighted bonding trends in these complex open-shell systems consistent with the spectroscopic information. The data indicate that larger clusters (n>5) have significant non-covalent bonding character and are likely to be kinetically unstable, in agreement with the cluster mass distribution obtained in gas-aggregation source experiments. The spectral fingerprints of the different clusters obtained from our calculations also suggest that identification of specific BinC2n+ structural isomers should be possible based on infra-red and optical absorption spectroscopy.

AB - Vibrational and electronic absorption spectra calculated at the (time-dependent) density functional theory level for the bismuth carbide clusters BinC2n+ (3⩽n⩽9) indicate significant differences in types of bonding that depend on cluster geometry. Analysis of the electronic charge densities of these clusters highlighted bonding trends in these complex open-shell systems consistent with the spectroscopic information. The data indicate that larger clusters (n>5) have significant non-covalent bonding character and are likely to be kinetically unstable, in agreement with the cluster mass distribution obtained in gas-aggregation source experiments. The spectral fingerprints of the different clusters obtained from our calculations also suggest that identification of specific BinC2n+ structural isomers should be possible based on infra-red and optical absorption spectroscopy.

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KW - Spectroscopy

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First-principles characterisation of spectroscopic and bonding properties of cationic bismuth carbide clusters

Abstract

Bibliographical note

Data Availability Statement

Keywords

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