Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a Site of T 
 h symmetry: Pr 
 3+ in Cs
 2NaPr(NO
 2)
 6

Wenyu Li; Lixin Ning; Michèle D. Faucher; Peter A. Tanner

doi:10.1021/ic201225k

Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a Site of T h symmetry: Pr 3+ in Cs 2NaPr(NO 2) 6

Wenyu Li
, Lixin Ning
, Michèle D. Faucher
, Peter A. Tanner

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

7 Citations (Scopus)

Abstract

The Pr ³⁺ ion in Cs ₂NaPr(NO ₂) ₆ is situated at a site of T _h symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr ³⁺ 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core. The ¹D ₂ → ³H ₄ emission spectra of Cs ₂NaPr(NO ₂) ₆ at 7 K enabled assignments to be made for the crystal-field (CF) levels of the ground-state multiplet. The emission of the dilute system Cs ₂NaY(NO ₂) ₆:Pr ³⁺ was dominated by NO ₂ ^- triplet emission, which was quenched at elevated temperatures by energy transfer to trace Eu ³⁺ impurity. From magnetic dipole calculations and the vibronic fingerprint, detailed assignments are given for the complex 10 K electronic absorption spectrum of Cs ₂NaPr(NO ₂) ₆ between 3940 and 18800 cm ^-1, and the derived Pr ³⁺ 4f ² energy-level data set has been fitted by calculation. By comparison with Cs ₂NaPrCl ₆, the fourth-order CF parameter in Cs ₂NaPr(NO ₂) ₆ is relatively small so that interaction with a 4fnp configuration is not important. From the NO ₂ ^- absorption bands above 20 000 cm ^-1, the N-O bond length change upon excitation is small, whereas the angle O-N-O opens by more than 10° in the triplet state. By contrast to the NO ₂ ^- internal vibration frequencies, which except for the wagging mode show only minor changes with the environment, the triplet-state energy shows a linear decrease with an increase of the lanthanide (Ln ³⁺) ionic radius in Cs ₂NaLn(NO ₂) ₆. Using the eigenvectors from the energy-level fit, the variation of the inverse magnetic susceptibility with temperature has been calculated between 1 and 100 K and the values are somewhat lower than those from experiment. © 2011 American Chemical Society.

Original language	English
Pages (from-to)	9004-9013
Journal	Inorganic Chemistry
Volume	50
Issue number	18
DOIs	https://doi.org/10.1021/ic201225k
Publication status	Published - 19 Sept 2011

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@article{fb7e69e13cb24a11866eb85262010574,

title = "Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a Site of T h symmetry: Pr 3+ in Cs 2NaPr(NO 2) 6",

abstract = "The Pr 3+ ion in Cs 2NaPr(NO 2) 6 is situated at a site of T h symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr 3+ 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core. The 1D 2 → 3H 4 emission spectra of Cs 2NaPr(NO 2) 6 at 7 K enabled assignments to be made for the crystal-field (CF) levels of the ground-state multiplet. The emission of the dilute system Cs 2NaY(NO 2) 6:Pr 3+ was dominated by NO 2 - triplet emission, which was quenched at elevated temperatures by energy transfer to trace Eu 3+ impurity. From magnetic dipole calculations and the vibronic fingerprint, detailed assignments are given for the complex 10 K electronic absorption spectrum of Cs 2NaPr(NO 2) 6 between 3940 and 18800 cm -1, and the derived Pr 3+ 4f 2 energy-level data set has been fitted by calculation. By comparison with Cs 2NaPrCl 6, the fourth-order CF parameter in Cs 2NaPr(NO 2) 6 is relatively small so that interaction with a 4fnp configuration is not important. From the NO 2 - absorption bands above 20 000 cm -1, the N-O bond length change upon excitation is small, whereas the angle O-N-O opens by more than 10° in the triplet state. By contrast to the NO 2 - internal vibration frequencies, which except for the wagging mode show only minor changes with the environment, the triplet-state energy shows a linear decrease with an increase of the lanthanide (Ln 3+) ionic radius in Cs 2NaLn(NO 2) 6. Using the eigenvectors from the energy-level fit, the variation of the inverse magnetic susceptibility with temperature has been calculated between 1 and 100 K and the values are somewhat lower than those from experiment. {\textcopyright} 2011 American Chemical Society.",

author = "Wenyu Li and Lixin Ning and Faucher, \{Mich{\`e}le D.\} and Tanner, \{Peter A.\}",

year = "2011",

month = sep,

day = "19",

doi = "10.1021/ic201225k",

language = "English",

volume = "50",

pages = "9004--9013",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "18",

}

Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a Site of T h symmetry: Pr 3+ in Cs 2NaPr(NO 2) 6. / Li, Wenyu; Ning, Lixin; Faucher, Michèle D. et al.
In: Inorganic Chemistry, Vol. 50, No. 18, 19.09.2011, p. 9004-9013.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a Site of T h symmetry

T2 - Pr 3+ in Cs 2NaPr(NO 2) 6

AU - Li, Wenyu

AU - Ning, Lixin

AU - Faucher, Michèle D.

AU - Tanner, Peter A.

PY - 2011/9/19

Y1 - 2011/9/19

N2 - The Pr 3+ ion in Cs 2NaPr(NO 2) 6 is situated at a site of T h symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr 3+ 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core. The 1D 2 → 3H 4 emission spectra of Cs 2NaPr(NO 2) 6 at 7 K enabled assignments to be made for the crystal-field (CF) levels of the ground-state multiplet. The emission of the dilute system Cs 2NaY(NO 2) 6:Pr 3+ was dominated by NO 2 - triplet emission, which was quenched at elevated temperatures by energy transfer to trace Eu 3+ impurity. From magnetic dipole calculations and the vibronic fingerprint, detailed assignments are given for the complex 10 K electronic absorption spectrum of Cs 2NaPr(NO 2) 6 between 3940 and 18800 cm -1, and the derived Pr 3+ 4f 2 energy-level data set has been fitted by calculation. By comparison with Cs 2NaPrCl 6, the fourth-order CF parameter in Cs 2NaPr(NO 2) 6 is relatively small so that interaction with a 4fnp configuration is not important. From the NO 2 - absorption bands above 20 000 cm -1, the N-O bond length change upon excitation is small, whereas the angle O-N-O opens by more than 10° in the triplet state. By contrast to the NO 2 - internal vibration frequencies, which except for the wagging mode show only minor changes with the environment, the triplet-state energy shows a linear decrease with an increase of the lanthanide (Ln 3+) ionic radius in Cs 2NaLn(NO 2) 6. Using the eigenvectors from the energy-level fit, the variation of the inverse magnetic susceptibility with temperature has been calculated between 1 and 100 K and the values are somewhat lower than those from experiment. © 2011 American Chemical Society.

AB - The Pr 3+ ion in Cs 2NaPr(NO 2) 6 is situated at a site of T h symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr 3+ 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core. The 1D 2 → 3H 4 emission spectra of Cs 2NaPr(NO 2) 6 at 7 K enabled assignments to be made for the crystal-field (CF) levels of the ground-state multiplet. The emission of the dilute system Cs 2NaY(NO 2) 6:Pr 3+ was dominated by NO 2 - triplet emission, which was quenched at elevated temperatures by energy transfer to trace Eu 3+ impurity. From magnetic dipole calculations and the vibronic fingerprint, detailed assignments are given for the complex 10 K electronic absorption spectrum of Cs 2NaPr(NO 2) 6 between 3940 and 18800 cm -1, and the derived Pr 3+ 4f 2 energy-level data set has been fitted by calculation. By comparison with Cs 2NaPrCl 6, the fourth-order CF parameter in Cs 2NaPr(NO 2) 6 is relatively small so that interaction with a 4fnp configuration is not important. From the NO 2 - absorption bands above 20 000 cm -1, the N-O bond length change upon excitation is small, whereas the angle O-N-O opens by more than 10° in the triplet state. By contrast to the NO 2 - internal vibration frequencies, which except for the wagging mode show only minor changes with the environment, the triplet-state energy shows a linear decrease with an increase of the lanthanide (Ln 3+) ionic radius in Cs 2NaLn(NO 2) 6. Using the eigenvectors from the energy-level fit, the variation of the inverse magnetic susceptibility with temperature has been calculated between 1 and 100 K and the values are somewhat lower than those from experiment. © 2011 American Chemical Society.

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U2 - 10.1021/ic201225k

DO - 10.1021/ic201225k

M3 - RGC 21 - Publication in refereed journal

SN - 0020-1669

VL - 50

SP - 9004

EP - 9013

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 18

ER -