Computational and experimental studies of the electronic excitation spectra of EDTA and DTPA substituted tetraphenylporphyrins and their Lu complexes

Rashid R. Valiev, Elena G. Ermolina, Rimma T. Kuznetsova, Victor N. Cherepanov, Dage Sundholm

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

Ethylendiaminetetraacetic acid (EDTA) substituted and diethylenetriaminopentaacetic acid (DTPA) substituted aminated free-base tetraphenylporphyrins (H2ATPP) and the corresponding lutetium(III) complexes have been studied computationally at the density functional theory (DFT) and second-order algebraic diagrammatic construction (ADC(2)) levels using triple-ξ basis sets augmented with polarization functions. The molecular structures were optimized using Becke's three-parameter hybrid functional (B3LYP). The electronic excitation spectra in the range of 400-700 nm were calculated using the ADC(2) and the linear-response time-dependent DFT methods. The calculated spectra are compared to those measured in ethanol solution. The calculated excitation energies agree well with those deduced from the experimental spectra. The excitation energies for the Qx band calculated at the B3LYP and ADC(2) level are 0.20-0.25 eV larger than the experimental values. The excitation energies for the Qy band calculated at the B3LYP level are 0.10-0.20 eV smaller than the ADC(2) ones and are thus in good agreement with experiment. The calculated excitation energies corresponding to the Bx and By bands are 0.10-0.30 eV larger than the experimental values. The excitation energies of the B x and By bands calculated at the B3LYP level are in somewhat better agreement with experiment than the ADC(2) ones. The calculated and measured band strengths largely agree.

Original languageEnglish
Pages (from-to)4631-4637
Number of pages7
JournalJournal of Molecular Modeling
Volume19
Issue number11
DOIs
Publication statusPublished - Nov 2013

Fingerprint

Excitation energy
acids
Acids
electronics
excitation
Density functional theory
Lutetium
energy
density functional theory
lutetium
Molecular structure
Ethanol
Experiments
tetraphenylporphyrin
Polarization
ethyl alcohol
molecular structure
polarization

Keywords

  • Ethylendiaminetetraacetic acid
  • Tetraphenylporphyrins
  • The approximate second-order coupled-cluster

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computer Science Applications
  • Computational Theory and Mathematics
  • Catalysis
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Computational and experimental studies of the electronic excitation spectra of EDTA and DTPA substituted tetraphenylporphyrins and their Lu complexes. / Valiev, Rashid R.; Ermolina, Elena G.; Kuznetsova, Rimma T.; Cherepanov, Victor N.; Sundholm, Dage.

In: Journal of Molecular Modeling, Vol. 19, No. 11, 11.2013, p. 4631-4637.

Research output: Contribution to journalArticle

Valiev, Rashid R. ; Ermolina, Elena G. ; Kuznetsova, Rimma T. ; Cherepanov, Victor N. ; Sundholm, Dage. / Computational and experimental studies of the electronic excitation spectra of EDTA and DTPA substituted tetraphenylporphyrins and their Lu complexes. In: Journal of Molecular Modeling. 2013 ; Vol. 19, No. 11. pp. 4631-4637.
@article{c26295da5a1446f4b87f3a59efd68eeb,
title = "Computational and experimental studies of the electronic excitation spectra of EDTA and DTPA substituted tetraphenylporphyrins and their Lu complexes",
abstract = "Ethylendiaminetetraacetic acid (EDTA) substituted and diethylenetriaminopentaacetic acid (DTPA) substituted aminated free-base tetraphenylporphyrins (H2ATPP) and the corresponding lutetium(III) complexes have been studied computationally at the density functional theory (DFT) and second-order algebraic diagrammatic construction (ADC(2)) levels using triple-ξ basis sets augmented with polarization functions. The molecular structures were optimized using Becke's three-parameter hybrid functional (B3LYP). The electronic excitation spectra in the range of 400-700 nm were calculated using the ADC(2) and the linear-response time-dependent DFT methods. The calculated spectra are compared to those measured in ethanol solution. The calculated excitation energies agree well with those deduced from the experimental spectra. The excitation energies for the Qx band calculated at the B3LYP and ADC(2) level are 0.20-0.25 eV larger than the experimental values. The excitation energies for the Qy band calculated at the B3LYP level are 0.10-0.20 eV smaller than the ADC(2) ones and are thus in good agreement with experiment. The calculated excitation energies corresponding to the Bx and By bands are 0.10-0.30 eV larger than the experimental values. The excitation energies of the B x and By bands calculated at the B3LYP level are in somewhat better agreement with experiment than the ADC(2) ones. The calculated and measured band strengths largely agree.",
keywords = "Ethylendiaminetetraacetic acid, Tetraphenylporphyrins, The approximate second-order coupled-cluster",
author = "Valiev, {Rashid R.} and Ermolina, {Elena G.} and Kuznetsova, {Rimma T.} and Cherepanov, {Victor N.} and Dage Sundholm",
year = "2013",
month = "11",
doi = "10.1007/s00894-012-1400-9",
language = "English",
volume = "19",
pages = "4631--4637",
journal = "Journal of Molecular Modeling",
issn = "1610-2940",
publisher = "Springer Verlag",
number = "11",

}

TY - JOUR

T1 - Computational and experimental studies of the electronic excitation spectra of EDTA and DTPA substituted tetraphenylporphyrins and their Lu complexes

AU - Valiev, Rashid R.

AU - Ermolina, Elena G.

AU - Kuznetsova, Rimma T.

AU - Cherepanov, Victor N.

AU - Sundholm, Dage

PY - 2013/11

Y1 - 2013/11

N2 - Ethylendiaminetetraacetic acid (EDTA) substituted and diethylenetriaminopentaacetic acid (DTPA) substituted aminated free-base tetraphenylporphyrins (H2ATPP) and the corresponding lutetium(III) complexes have been studied computationally at the density functional theory (DFT) and second-order algebraic diagrammatic construction (ADC(2)) levels using triple-ξ basis sets augmented with polarization functions. The molecular structures were optimized using Becke's three-parameter hybrid functional (B3LYP). The electronic excitation spectra in the range of 400-700 nm were calculated using the ADC(2) and the linear-response time-dependent DFT methods. The calculated spectra are compared to those measured in ethanol solution. The calculated excitation energies agree well with those deduced from the experimental spectra. The excitation energies for the Qx band calculated at the B3LYP and ADC(2) level are 0.20-0.25 eV larger than the experimental values. The excitation energies for the Qy band calculated at the B3LYP level are 0.10-0.20 eV smaller than the ADC(2) ones and are thus in good agreement with experiment. The calculated excitation energies corresponding to the Bx and By bands are 0.10-0.30 eV larger than the experimental values. The excitation energies of the B x and By bands calculated at the B3LYP level are in somewhat better agreement with experiment than the ADC(2) ones. The calculated and measured band strengths largely agree.

AB - Ethylendiaminetetraacetic acid (EDTA) substituted and diethylenetriaminopentaacetic acid (DTPA) substituted aminated free-base tetraphenylporphyrins (H2ATPP) and the corresponding lutetium(III) complexes have been studied computationally at the density functional theory (DFT) and second-order algebraic diagrammatic construction (ADC(2)) levels using triple-ξ basis sets augmented with polarization functions. The molecular structures were optimized using Becke's three-parameter hybrid functional (B3LYP). The electronic excitation spectra in the range of 400-700 nm were calculated using the ADC(2) and the linear-response time-dependent DFT methods. The calculated spectra are compared to those measured in ethanol solution. The calculated excitation energies agree well with those deduced from the experimental spectra. The excitation energies for the Qx band calculated at the B3LYP and ADC(2) level are 0.20-0.25 eV larger than the experimental values. The excitation energies for the Qy band calculated at the B3LYP level are 0.10-0.20 eV smaller than the ADC(2) ones and are thus in good agreement with experiment. The calculated excitation energies corresponding to the Bx and By bands are 0.10-0.30 eV larger than the experimental values. The excitation energies of the B x and By bands calculated at the B3LYP level are in somewhat better agreement with experiment than the ADC(2) ones. The calculated and measured band strengths largely agree.

KW - Ethylendiaminetetraacetic acid

KW - Tetraphenylporphyrins

KW - The approximate second-order coupled-cluster

UR - http://www.scopus.com/inward/record.url?scp=84888299066&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84888299066&partnerID=8YFLogxK

U2 - 10.1007/s00894-012-1400-9

DO - 10.1007/s00894-012-1400-9

M3 - Article

C2 - 22447238

AN - SCOPUS:84888299066

VL - 19

SP - 4631

EP - 4637

JO - Journal of Molecular Modeling

JF - Journal of Molecular Modeling

SN - 1610-2940

IS - 11

ER -