| Title: |
Vibrational dynamics of iron pentacarbonyl [Fe(CO)5] in liquid alkanes revisited. |
| Authors: |
Jouan, Armel; Jonusas, Mindaugas; Vincent, Julien; Bernhardt, Sylvie; Tauvy, Michel; Jacquart, Marc; Helbing, Jan; Chin, Wutharath; Crépin, Claudine |
| Source: |
Journal of Chemical Physics; 6/21/2025, Vol. 162 Issue 23, p1-10, 10p |
| Subject Terms: |
ANHARMONIC motion; VISCOSITY; ANISOTROPY; ALKANES; SOLVENTS |
| Abstract: |
We explore the solvent-dependence of the vibrational dynamics of Fe(CO)5 (IPC) using a novel 2D-IR setup. A 320 pixel MCT camera allows us to achieve high spectral resolution within a large detection window, which can be matched in excitation by scanning coherence times of up to 250 ps. The dynamics of the IR active modes of IPC in the C≡O stretching range are probed in a series of alkanes of different chain lengths and viscosities. 2D-IR maps at short waiting times reveal the detailed anharmonic structure of the modes at play: we determined the cross-anharmonicity between the A 2 ″ and E′ modes (δ = −0.8 ± 0.1 cm−1), and we are able to differentiate the diagonal anharmonicity of the doubly degenerate mode (ΔE ≃ 18 cm−1) from its non-diagonal anharmonicity (ΔEE ≃ 11 cm−1). Our analysis of the polarization dependence of the 2D-IR signals strongly confirms an exchange mechanism between the IR-active modes due to Berry pseudo-rotation, which shows very little dependence on solvent viscosity, in contrast to the anisotropy loss. The implications of our findings for the exchange mechanism are discussed. [ABSTRACT FROM AUTHOR] |
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| Database: |
Complementary Index |