Abstract
A gas-phase electronic spectrum of nicotine in a supersonic expansion has been recorded using two-color resonant two-photon ionization spectroscopy. Efficient photoionization was achievable only via the pyridine chromophore owing to poor Franck-Condon overlap in the N-methylpyrrolidine moiety. Two conformers of nicotine have been characterized and assigned by infrared-ultraviolet (IR-UV) ion depletion and IR-UV hole-burning spectroscopy, in combination with quantum chemical techniques. Trans-A with nitrogen atoms further apart is more stable by 2 kJ mol-1 and the most populated conformer in the supersonic jet, owing this stability to a stronger inter-ring CH···N hydrogen bond than the trans-B counterpart.
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