(1 + 1) REMPI spectrum of 7AI-PhOH recorded with picosecond pulses (black trace). The lower spectrum (red trace) shows the Franck-Condon factors simulation of the electronic spectrum for this cluster with the vibrational frequencies calculated at the CC2 level, with the suggested assignment of some vibrational progressions.
Pump and probe signals recorded on the mass channel of the 7AI-PhOH+ ion, upon excitation to the 00 0 transition (a) and to the 00 0 +127 cm−1 transition (b). The probe wavelength was 306 nm. Upper trace: on-resonance excitation; middle trace: off-resonance excitation; and bottom trace: difference between on-resonance and off-resonance signals with their respective fitting to a pulse shape convoluted single exponential decay function.
(a) LIF spectrum measured by exciting with nanosecond pulses and detecting the total UV-vis fluorescence (black). The circles, triangles, and squares indicate the vibronic bands of the 7AI(H2O), 7AI(H2O)2, and 7AI(H2O)3 complexes, respectively. REMPI spectra of 7AI-PhOH (blue) and 7AI(H2O)1 (red) recorded with picosecond pulses, for comparison. (b) Mass spectrum recorded under the same experimental conditions that the LIF spectrum. The ionization was achieved with nanosecond pulses with the laser tuned on-resonance at 33 313 cm−1 (upper trace) and off-resonance at 33 250 cm−1 (lower trace).
Low frequency (a) 13 cm−1, (b) 150 cm−1, and (c) 258 cm−1 vibrational normal modes of the 7AI-PhOH complex, calculated at the RI-CC2/basis set pVDZ level.
Potential energy functions for the electronic ground state (S0) and the locally excited (S1) state of the 7AI-PhOH as a function of the concerted stretching of the O1H2/N1H1 distances. The optimized structures in different regions of the excited states function are shown in the lower part of the figure.
Potential energy function for the electronic ground state (S0), the locally excited (ππ*), and the charge-transfer excited (CT) states of the 7AI-PhOH, as a function of the O1H2 distance. The scheme of the orbitals involved in the transitions for the ππ* and CT states are shown in the lower part of the figure.
Experimental and calculated vibrational frequencies of the S1 state of 7AI-PhOH.
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