Femtosecond Infrared Coherent Excitation of Liquid Phase Vibrational Population Distributions (v [greater than] 5)
T Witte, J S. Yeston, Edwin J. Heilweil, K L. Kompa, M Motzkus
Irradiation of a hexane solution of W(CO)6 with femtosecond mid-IR pulses, resonant with the transition energies for the first seven steps in the anharmonic potential of the T1u CO-stretch, has transferred vibrational population up to at least v = 6. The overall population distribution in levels up to v = 5 has been measured, and the anharmonic ladder of the potential, including resonance frequencies and spectral broadening of the single transitions, has been characterized by transient absorption spectroscopy. For the molecule under consideration, reaching the level v = 6 corresponds to a total deposited energy in a single mode of up to 12000 cm-1, which is very close to the dissociation threshold of one M-C bond. These results thus constitute a significant step toward the initiation, and ultimately control, of MIR induced molecular ground state reactions in the condensed phase, which is most relevant for chemical reactions in general.
anharmonicity, coherent control, IR multiphoton excitation, metal carbonyl, mid-IR transient absorption, ultrafast spectroscopy, vibrational overtones
, Yeston, J.
, Heilweil, E.
, Kompa, K.
and Motzkus, M.
Femtosecond Infrared Coherent Excitation of Liquid Phase Vibrational Population Distributions (v [greater than] 5), Chemical Physics Letters, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=841774
(Accessed May 28, 2023)