Density-functional theory investigation of the geometric, energetic and optical properties of the cobalt(II)tris(2,2'-bipyridine) complex in the high-spin and in the Jahn-Teller active low-spin state

Vargas, Alfredo; Zerara, Mohamed; Krausz, Elmars; Hauser, Andreas; Lawson Daku, Latevi Max

doi:10.1021/ct6001384

Scientific article

English

Density-functional theory investigation of the geometric, energetic and optical properties of the cobalt(II)tris(2,2'-bipyridine) complex in the high-spin and in the Jahn-Teller active low-spin state

Contributors

Vargas, Alfredo; Zerara, Mohamed; Krausz, Elmars; Hauser, Andreas; Lawson Daku, Latevi Max

Published in

Journal of chemical theory and computation, vol. 2, no. 42, p. 1342-1359

Publication date

2006

Abstract

State-of-the-art generalized gradient approximation (GGA) (PBE, OPBE, RPBE, OLYP, and HCTH), meta-GGA (VSXC and TPSS), and hybrid (B3LYP, B3LYP*, O3LYP, and PBE0) functionals are compared for the determination of the structure and the energetics of the D3 [Co(bpy)3]2+ complex in the 4A2 and 4E trigonal components of the high-spin 4T1g( ) state and in the low-spin 2E state of octahedral 2Eg( ) parentage. Their comparison extends also to the investigation of the Jahn−Teller instability of the 2E state through the characterization of the extrema of C2 symmetry of this spin state's potential energy surface. The results obtained for [Co(bpy)3]2+ in either spin manifold are very consistent among the functionals used and are in good agreement with available experimental data. The functionals, however, perform very differently with respect to the spin-state energetics because the calculated values of the high-spin/low-spin energy difference Δ vary between −3212 and 3919 cm-1. Semilocal functionals tend to give too large Δ values and thus fail to correctly predict the high-spin state as the ground state of the isolated complex, while hybrid functionals tend to overestimate the stability of the high-spin state with respect to the low-spin state. Reliable results are, however, obtained with the OLYP, HCTH, B3LYP*, and O3LYP functionals which perform best for the description of the isolated complex. The optical properties of [Co(bpy)3]2+ in the two spin states are also analyzed on the basis of electronic excitation calculations performed within time-dependent density functional response theory. The calculated absorption and circular dichroism spectra agree well with experimental results.

UNIGE affiliation entities

Faculté des sciences / Section de chimie et biochimie / Département de chimie physique

UNIGE research groups

Groupe Hauser

Citation (ISO format)

VARGAS, Alfredo et al. Density-functional theory investigation of the geometric, energetic and optical properties of the cobalt(II)tris(2,2′-bipyridine) complex in the high-spin and in the Jahn-Teller active low-spin state. In: Journal of chemical theory and computation, 2006, vol. 2, n° 42, p. 1342–1359. doi: 10.1021/ct6001384

Article (Published version)

Identifiers

PID : unige:3638
DOI : 10.1021/ct6001384

Additional URL for this publication

http://pubs.acs.org/cgi-bin/article.cgi/jctcce/2006/2/i05/pdf/ct6001384.pdf

Journal ISSN

1549-9618

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Creation

02/10/2009 15:19:13

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02/10/2009 15:19:13

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14/03/2023 15:15:46

Status update

14/03/2023 15:15:46

Last indexation

10/06/2025 21:31:22

Density-functional theory investigation of the geometric, energetic and optical properties of the cobalt(II)tris(2,2'-bipyridine) complex in the high-spin and in the Jahn-Teller active low-spin state

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Published in

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Abstract

UNIGE affiliation entities

UNIGE research groups

Citation (ISO format)

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