Rydberg state mediated multiphoton ionization of (η⁷-C₇H₇)(η⁵-C₅H₅)Cr: DFT-supported experimental insights into the molecular and electronic structures of excited sandwich complexes

Abstract

The first REMPI/DFT study of a mixed sandwich complex reveals fine ligand effects on structural transformations accompanying electronic excitation.

Effect of a single methyl substituent on the electronic structure of cobaltocene studied by computationally assisted MATI spectroscopy

“…This accuracy is better than that obtained for (Cp) 2 Co with the local coupled-cluster method DLPNO-CCSD( T 0 ) using more extended basis sets. 73 Another DLPNO-CCSD( T 0 ) study of cobaltocene 85 produced the I ad value of 5.308 eV, which is very close to the MATI result (Table 1), but this calculation included a 350 K thermal correction that should be subtracted for comparison with the MATI data 28 obtained for jet-cooled molecules.…”

“…Good performance of the GGA functionals in estimating ionization energies of sandwich molecules has been noted earlier. 28,73,84,85 Among the DFT methods used in this work, the smallest I calc À I exp values of À0.05 to À0.06 eV were obtained with the meta-hybrid TPSSh functional (Table 1).…”

“…Therefore, it is preferable to compare calculated and experimental values of I ad rather than I vert . The vibronic peaks arising from the excitation of the metal-ligand stretching mode were also observed in the MATI spectra of (Z 6 -PhH) 2 Cr, 48,49 (Z 6 -PhMe)(Z 6 -PhH)Cr 57 and (Z 8 -C 8 H 8 )(Cp)Ti, 59 ZEKE spectra of (Z 6 -PhH) 2 M (M = Cr, Mo, W, Ti, V) 50,52 and (Z 6 -PhH)M 0 (M 0 = Y, La, Lu), 81 resonance-enhanced multiphoton ionization (REMPI) spectra of (Cp) 2 Fe, 82 (Z 6 -PhH) 2 Cr 83,84 and (Z 7 -C 7 H 7 )(Cp)Cr, 85 as well as in the laser-induced fluorescence spectra of unstable half-sandwich systems (Cp)M 00 and (Cp 0 )M 00 (M 00 = Mg, Ca, Zn, Cd). [86][87][88][89] The n 2 vibration (219 cm À1 ) revealed in the (Cp 0 )(Cp)Co MATI spectrum (Fig.…”

Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck-Condon Simulations

“…Kwon's group built a vacuum ultraviolet single photon MATI system to study many cationic vibrational features [22][23][24][25][26][27][28][29]. Tzeng's group and Ketkov's group used two-color MATI to study the cationic spectra of many benzene derivatives and sandwich molecules [30][31][32][33][34][35][36]. Wright's group used ZEKE technology to research cationic vibrational features of many halogenated benzene and their derivatives [37][38][39][40][41][42].…”

Vibronic and Cationic Features of 2-Fluorobenzonitrile and 3-Fluorobenzonitrile Studied by REMPI and MATI Spectroscopy and Franck–Condon Simulations

“…Kwon’s group built a vacuum ultraviolet single photon MATI system to study many cationic vibrational features [ 22 , 23 , 24 , 25 , 26 , 27 , 28 , 29 ]. Tzeng’s group and Ketkov’s group used two-color MATI to study the cationic spectra of many benzene derivatives and sandwich molecules [ 30 , 31 , 32 , 33 , 34 , 35 , 36 ]. Wright’s group used ZEKE technology to research cationic vibrational features of many halogenated benzene and their derivatives [ 37 , 38 , 39 , 40 , 41 , 42 ].…”