Isotope effects on the vibrational spectra of the Fe(Phen)2 (NCS)2 spin-crossover complex studied by density functional calculations

Villo K. Pälfi; Thomas Guillon; Hauke Paulsen; Gábor Molnár; Azzedine Bousseksou

doi:10.1016/j.crci.2004.11.032

Isotope effects on the vibrational spectra of the Fe(Phen)₂ (NCS)₂ spin-crossover complex studied by density functional calculations

Villo K. Pälfi, Thomas Guillon, Hauke Paulsen, Gábor Molnár, Azzedine Bousseksou^*

^*Korrespondierende/r Autor/-in für diese Arbeit

Institut für Physik

17 Zitate (Scopus)

Abstract

A geometry optimization and vibrational frequency calculation has been carried out on the Fe(phen)₂(NCS)₂ (phen = 1,10 phenantroline) molecule in both spin states (S = 0 and S = 2) using the density functional theory (DFT) method with the B3LYP functional and the 6-31G(d) basis set. The frequency shifts upon ⁵⁴Fe- ⁵⁷Fe and ¹⁴N-¹⁵N isotope substitutions have been calculated and compared with the experimental frequency shifts as well as with calculated data (DFT/BP86) published in the literature. In the low frequency region (100-600 cm^-1), both DFT methods reproduce correctly the measured isotope shifts. The accuracy of the calculated vibrational entropy change upon the spin crossover (SCO) is lower: reasonable errors (∼10%) of the calculated frequencies lead to a relatively large error (∼50%) of the total entropy change.

Originalsprache	Englisch
Zeitschrift	Comptes Rendus Chimie
Jahrgang	8
Ausgabenummer	8 SPEC. ISS.
Seiten (von - bis)	1317-1325
Seitenumfang	9
ISSN	1631-0748
DOIs	https://doi.org/10.1016/j.crci.2004.11.032
Publikationsstatus	Veröffentlicht - 01.08.2005

Fördermittel

The authors are grateful for a European Commission Marie-Curie Fellowship (Villő K. Palfi) and the Calculs en Midi-Pyrenées (CALMIP, Toulouse, France) supercomputer center for calculation facilities.

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SDG 9 – Industrie, Innovation und Infrastruktur

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10.1016/j.crci.2004.11.032

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title = "Isotope effects on the vibrational spectra of the Fe(Phen)2 (NCS)2 spin-crossover complex studied by density functional calculations",

abstract = "A geometry optimization and vibrational frequency calculation has been carried out on the Fe(phen)2(NCS)2 (phen = 1,10 phenantroline) molecule in both spin states (S = 0 and S = 2) using the density functional theory (DFT) method with the B3LYP functional and the 6-31G(d) basis set. The frequency shifts upon 54Fe- 57Fe and 14N-15N isotope substitutions have been calculated and compared with the experimental frequency shifts as well as with calculated data (DFT/BP86) published in the literature. In the low frequency region (100-600 cm-1), both DFT methods reproduce correctly the measured isotope shifts. The accuracy of the calculated vibrational entropy change upon the spin crossover (SCO) is lower: reasonable errors (∼10\%) of the calculated frequencies lead to a relatively large error (∼50\%) of the total entropy change.",

author = "P{\"a}lfi, \{Villo K.\} and Thomas Guillon and Hauke Paulsen and G{\'a}bor Moln{\'a}r and Azzedine Bousseksou",

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Isotope effects on the vibrational spectra of the Fe(Phen)₂ (NCS)₂ spin-crossover complex studied by density functional calculations. / Pälfi, Villo K.; Guillon, Thomas; Paulsen, Hauke et al.
in: Comptes Rendus Chimie, Jahrgang 8, Nr. 8 SPEC. ISS., 01.08.2005, S. 1317-1325.

Publikation: Beiträge in Fachzeitschriften › Zeitschriftenaufsätze › Forschung › Begutachtung

TY - JOUR

T1 - Isotope effects on the vibrational spectra of the Fe(Phen)2 (NCS)2 spin-crossover complex studied by density functional calculations

AU - Pälfi, Villo K.

AU - Guillon, Thomas

AU - Paulsen, Hauke

AU - Molnár, Gábor

AU - Bousseksou, Azzedine

PY - 2005/8/1

Y1 - 2005/8/1

N2 - A geometry optimization and vibrational frequency calculation has been carried out on the Fe(phen)2(NCS)2 (phen = 1,10 phenantroline) molecule in both spin states (S = 0 and S = 2) using the density functional theory (DFT) method with the B3LYP functional and the 6-31G(d) basis set. The frequency shifts upon 54Fe- 57Fe and 14N-15N isotope substitutions have been calculated and compared with the experimental frequency shifts as well as with calculated data (DFT/BP86) published in the literature. In the low frequency region (100-600 cm-1), both DFT methods reproduce correctly the measured isotope shifts. The accuracy of the calculated vibrational entropy change upon the spin crossover (SCO) is lower: reasonable errors (∼10%) of the calculated frequencies lead to a relatively large error (∼50%) of the total entropy change.

AB - A geometry optimization and vibrational frequency calculation has been carried out on the Fe(phen)2(NCS)2 (phen = 1,10 phenantroline) molecule in both spin states (S = 0 and S = 2) using the density functional theory (DFT) method with the B3LYP functional and the 6-31G(d) basis set. The frequency shifts upon 54Fe- 57Fe and 14N-15N isotope substitutions have been calculated and compared with the experimental frequency shifts as well as with calculated data (DFT/BP86) published in the literature. In the low frequency region (100-600 cm-1), both DFT methods reproduce correctly the measured isotope shifts. The accuracy of the calculated vibrational entropy change upon the spin crossover (SCO) is lower: reasonable errors (∼10%) of the calculated frequencies lead to a relatively large error (∼50%) of the total entropy change.

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