Vibrational spectroscopy of Cu⁺(H₂)₄: about anharmonicity and fluxionality

Abstract

The vibrational spectra of the copper(i) cation–dihydrogen complexes Cu+(H2)4, Cu+(D2)4 and Cu+(D2)3H2 are studied using cryogenic ion trap vibrational spectroscopy in combination with quantum chemical calculations.

Vibrational wave-packet dynamics of the silver pentamer probed by femtosecond NeNePo spectroscopy

“…15 Furthermore, previously reported fs NeNePo transients of Ag 2 reveal FT bands at a lower wavenumber (redshifted) compared to vibrational energies measured in the gas phase, due to the combination of vibrational anharmonicity and the population of higher-lying vibrational states. 37,38 The frequency resolution of the present FT spectra is around 4.2 cm À1 , given by the delay time range of the transient spectra of 8 ps. The reported n 1 frequency in solid argon (162 cm À1 ) is slightly higher that the FT band position (157 cm À1 ) obtained in the present study.…”

“…The fs NeNePo transients were measured using a tandem mass spectrometer with an integrated, cryogenically cooled linear quadrupole ion trap and an Ti:sapphire femtosecond laser system, as described previously. 38 Briefly, Ag 5…”

“…46 Recently, fs NeNePo studies on the silver dimer demonstrated that also higher-order vibrational constants of the electronic ground state X 1 S + g can be determined isotopologue specifically. 38 Here, we report our study on the vibrational wave-packet dynamics of the neutral silver pentamer probed by fs NeNePo spectroscopy. Fs NeNePo transients of Ag 5 obtained by different pump wavelengths (402 nm and 510 nm) reveal oscillatory Ag 5 + cation signals for the first time.…”

“…Furthermore, the temporal features of the pump-probe spectrum around time zero and the window spectrogram as a function of the delay time uncover the transient dynamics of photodetachment and vibrational energy redistribution in the neutral cluster. Fs NeNePo spectroscopy has been mainly applied to study the wave-packet dynamics of neutral metals as well as metal-containing clusters, namely, Ag n (n = 2-5 and 9), 27,[36][37][38][39][40][41][42] Ag 2 Á O 2 , 37 Ag 2 Au, 43 Cu(H 2 O) 1,2 , 44,45 and Cu(CD 3 OD). 46 Recently, fs NeNePo studies on the silver dimer demonstrated that also higher-order vibrational constants of the electronic ground state X 1 S + g can be determined isotopologue specifically.…”

Influence of Metal Identity in Bipyridine-Based Metal-4N Complexes With Formate

“…In addition, cryogenic preparation of the target ions allows suppression of thermal broadening. Cryogenic ion vibrational spectroscopy (CIVS) has been used to great success by many groups − and today represents a powerful part of the toolbox of cold chemistry.…”