Theoretical assessment of TD-DFT applied to a ferrocene-based complex

Mauricio Yáñez-S, Sergio A. Moya, César Zúñiga, Gloria Cárdenas-Jirón

Resultado de la investigación: Article

4 Citas (Scopus)

Resumen

We present a theoretical study of the electronic absorption spectrum of the 2-ferrocenyl-1,8-naphthyridine (FcNP) complex using the time-dependent density functional theory (TD-DFT) approach. The calculations were carried out at the DFT/LANL2DZ(Fe)/6-31++G(d) level of theory with nine DFT functionals of the type GGA (PBE, B97D), HGGA (B3LYP, PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP, LC-wPBE) in the condensed phase (CH2Cl2). The experimental spectrum for FcNP presents three electronic absorption bands (A, B, C) in the UV region and one band (D) in the visible region. We found that there is no unique functional that reproduces the entire electronic spectrum. GGA and LC-wPBE functionals predict large errors (up to 0.57 eV) for the UV bands. On the contrary, HGGA (PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP) functionals give small errors for these bands, 0.18, 0.12 and 0.25 eV, respectively. Band D is well described by all the functionals with errors up to 0.26 eV, except by the M05 and M06 functionals, which fail in this region with significant errors (0.52 and 0.56 eV). The analysis of the excitation energies shows that the PBE0, wB97XD and CAM-B3LYP functionals predict the best agreement with the experimental data. The two stronger bands (A, B) in the UV region are assigned to a ligand–ligand charge transfer (L-LCT) that involves the cyclopentadienyl rings (Cp) and the naphthyridine fragment (NP), and then associated with π → π electronic transitions. The two weaker bands (C, D) are assigned to a charge transfer from ligand (Cp) to metal (Fe)-ligand (NP) (L-MLCT) which is mainly addressed through the dxy and dz2 atomic orbitals, respectively. No charge transfer is observed between metal and NP ligand. It was shown that the theoretical methods used for understanding the electronic absorption properties of FcNP were adequate because the results showed an excellent agreement with experimental ones.

Idioma originalEnglish
Páginas (desde-hasta)65-74
Número de páginas10
PublicaciónComputational and Theoretical Chemistry
Volumen1118
DOI
EstadoPublished - 15 oct 2017

Huella dactilar

Naphthyridines
functionals
Density functional theory
density functional theory
computer aided manufacturing
Computer aided manufacturing
Charge transfer
charge transfer
fragments
Ligands
Discrete Fourier transforms
electronic spectra
ligands
Absorption spectra
Metals
electronics
absorption spectra
Excitation energy
metals
ferrocene

ASJC Scopus subject areas

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Citar esto

Yáñez-S, Mauricio ; Moya, Sergio A. ; Zúñiga, César ; Cárdenas-Jirón, Gloria. / Theoretical assessment of TD-DFT applied to a ferrocene-based complex. En: Computational and Theoretical Chemistry. 2017 ; Vol. 1118. pp. 65-74.
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abstract = "We present a theoretical study of the electronic absorption spectrum of the 2-ferrocenyl-1,8-naphthyridine (FcNP) complex using the time-dependent density functional theory (TD-DFT) approach. The calculations were carried out at the DFT/LANL2DZ(Fe)/6-31++G(d) level of theory with nine DFT functionals of the type GGA (PBE, B97D), HGGA (B3LYP, PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP, LC-wPBE) in the condensed phase (CH2Cl2). The experimental spectrum for FcNP presents three electronic absorption bands (A, B, C) in the UV region and one band (D) in the visible region. We found that there is no unique functional that reproduces the entire electronic spectrum. GGA and LC-wPBE functionals predict large errors (up to 0.57 eV) for the UV bands. On the contrary, HGGA (PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP) functionals give small errors for these bands, 0.18, 0.12 and 0.25 eV, respectively. Band D is well described by all the functionals with errors up to 0.26 eV, except by the M05 and M06 functionals, which fail in this region with significant errors (0.52 and 0.56 eV). The analysis of the excitation energies shows that the PBE0, wB97XD and CAM-B3LYP functionals predict the best agreement with the experimental data. The two stronger bands (A, B) in the UV region are assigned to a ligand–ligand charge transfer (L-LCT) that involves the cyclopentadienyl rings (Cp) and the naphthyridine fragment (NP), and then associated with π → π∗ electronic transitions. The two weaker bands (C, D) are assigned to a charge transfer from ligand (Cp) to metal (Fe)-ligand (NP) (L-MLCT) which is mainly addressed through the dxy and dz2 atomic orbitals, respectively. No charge transfer is observed between metal and NP ligand. It was shown that the theoretical methods used for understanding the electronic absorption properties of FcNP were adequate because the results showed an excellent agreement with experimental ones.",
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Theoretical assessment of TD-DFT applied to a ferrocene-based complex. / Yáñez-S, Mauricio; Moya, Sergio A.; Zúñiga, César; Cárdenas-Jirón, Gloria.

En: Computational and Theoretical Chemistry, Vol. 1118, 15.10.2017, p. 65-74.

Resultado de la investigación: Article

TY - JOUR

T1 - Theoretical assessment of TD-DFT applied to a ferrocene-based complex

AU - Yáñez-S, Mauricio

AU - Moya, Sergio A.

AU - Zúñiga, César

AU - Cárdenas-Jirón, Gloria

PY - 2017/10/15

Y1 - 2017/10/15

N2 - We present a theoretical study of the electronic absorption spectrum of the 2-ferrocenyl-1,8-naphthyridine (FcNP) complex using the time-dependent density functional theory (TD-DFT) approach. The calculations were carried out at the DFT/LANL2DZ(Fe)/6-31++G(d) level of theory with nine DFT functionals of the type GGA (PBE, B97D), HGGA (B3LYP, PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP, LC-wPBE) in the condensed phase (CH2Cl2). The experimental spectrum for FcNP presents three electronic absorption bands (A, B, C) in the UV region and one band (D) in the visible region. We found that there is no unique functional that reproduces the entire electronic spectrum. GGA and LC-wPBE functionals predict large errors (up to 0.57 eV) for the UV bands. On the contrary, HGGA (PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP) functionals give small errors for these bands, 0.18, 0.12 and 0.25 eV, respectively. Band D is well described by all the functionals with errors up to 0.26 eV, except by the M05 and M06 functionals, which fail in this region with significant errors (0.52 and 0.56 eV). The analysis of the excitation energies shows that the PBE0, wB97XD and CAM-B3LYP functionals predict the best agreement with the experimental data. The two stronger bands (A, B) in the UV region are assigned to a ligand–ligand charge transfer (L-LCT) that involves the cyclopentadienyl rings (Cp) and the naphthyridine fragment (NP), and then associated with π → π∗ electronic transitions. The two weaker bands (C, D) are assigned to a charge transfer from ligand (Cp) to metal (Fe)-ligand (NP) (L-MLCT) which is mainly addressed through the dxy and dz2 atomic orbitals, respectively. No charge transfer is observed between metal and NP ligand. It was shown that the theoretical methods used for understanding the electronic absorption properties of FcNP were adequate because the results showed an excellent agreement with experimental ones.

AB - We present a theoretical study of the electronic absorption spectrum of the 2-ferrocenyl-1,8-naphthyridine (FcNP) complex using the time-dependent density functional theory (TD-DFT) approach. The calculations were carried out at the DFT/LANL2DZ(Fe)/6-31++G(d) level of theory with nine DFT functionals of the type GGA (PBE, B97D), HGGA (B3LYP, PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP, LC-wPBE) in the condensed phase (CH2Cl2). The experimental spectrum for FcNP presents three electronic absorption bands (A, B, C) in the UV region and one band (D) in the visible region. We found that there is no unique functional that reproduces the entire electronic spectrum. GGA and LC-wPBE functionals predict large errors (up to 0.57 eV) for the UV bands. On the contrary, HGGA (PBE0), HMGGA (M05, M06) and range-separated (wB97XD, CAM-B3LYP) functionals give small errors for these bands, 0.18, 0.12 and 0.25 eV, respectively. Band D is well described by all the functionals with errors up to 0.26 eV, except by the M05 and M06 functionals, which fail in this region with significant errors (0.52 and 0.56 eV). The analysis of the excitation energies shows that the PBE0, wB97XD and CAM-B3LYP functionals predict the best agreement with the experimental data. The two stronger bands (A, B) in the UV region are assigned to a ligand–ligand charge transfer (L-LCT) that involves the cyclopentadienyl rings (Cp) and the naphthyridine fragment (NP), and then associated with π → π∗ electronic transitions. The two weaker bands (C, D) are assigned to a charge transfer from ligand (Cp) to metal (Fe)-ligand (NP) (L-MLCT) which is mainly addressed through the dxy and dz2 atomic orbitals, respectively. No charge transfer is observed between metal and NP ligand. It was shown that the theoretical methods used for understanding the electronic absorption properties of FcNP were adequate because the results showed an excellent agreement with experimental ones.

KW - Ferrocene

KW - Functional

KW - Naphthyridine

KW - TD-DFT

KW - UV–Vis

UR - http://www.scopus.com/inward/record.url?scp=85031307443&partnerID=8YFLogxK

U2 - 10.1016/j.comptc.2017.08.032

DO - 10.1016/j.comptc.2017.08.032

M3 - Article

AN - SCOPUS:85031307443

VL - 1118

SP - 65

EP - 74

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

ER -