Local force constants and charges of the nitrosyl ligand in photoinduced NO linkage isomers in a prototypical ruthenium nitrosyl complex.
Phys Chem Chem Phys
; 26(21): 15255-15267, 2024 May 29.
Article
em En
| MEDLINE
| ID: mdl-38751356
ABSTRACT
Photoinduced linkage isomers (PLI) of the NO ligand in transition-metal nitrosyl compounds can be identified by vibrational spectroscopy due to the large shifts of the î¡(NO) stretching vibration. We present a detailed experimental and theoretical study of the prototypical compound K2[RuCl5NO], where î¡(NO) shifts by ≈150 cm-1 when going from the N-bound (κN) ground state (GS) to the oxygen-bound (κO) metastable linkage isomer MS1, and by ≈360 cm-1 when going to the side-on (κ2N,O) metastable linkage isomer MS2. We show that the experimentally observed N-O stretching modes of the GS, MS1, and MS2 exhibit strong coupling with the Ru-N and Ru-O stretching modes, which can be decoupled using the local mode vibrational theory formalism. From the resulting decoupled pure two-atomic harmonic oscillators the local force constants are determined, which all follow the same quadratic behavior on the wavenumber. A Bader charge analysis shows that the total charge on the NO ligand is not correlated to the observed frequency shift of î¡(NO).
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Coleções:
01-internacional
Base de dados:
MEDLINE
Idioma:
En
Revista:
Phys Chem Chem Phys
Assunto da revista:
BIOFISICA
/
QUIMICA
Ano de publicação:
2024
Tipo de documento:
Article
País de afiliação:
França