TY - JOUR
T1 - Mapping multidimensional excited state dynamics using pump-impulsive- vibrational-spectroscopy and pump-degenerate-four-wave-mixing
AU - Kraack, Jan Philip
AU - Wand, Amir
AU - Buckup, Tiago
AU - Motzkus, Marcus
AU - Ruhman, Sanford
PY - 2013/9/14
Y1 - 2013/9/14
N2 - Pump-impulsive vibrational spectroscopy (pump-IVS) is used to record excited state vibrational dynamics following photoexcitation of two carotenoids, β-carotene and lycopene, with <30 fs temporal resolution, and covering the full vibrational spectrum of the investigated chromophores. The results record the course of S2-S1 internal conversion, followed by vibrational relaxation and decay to the electronic ground state. This interpretation is corroborated by comparison with pump-degenerate-four-wave- mixing (pump-DFWM) experiments on the same systems. The results demonstrate the potential of both time-domain spectroscopic techniques to resolve photochemical dynamics, including fingerprint frequencies which directly reflect changes in bonding and structure in the nascent sample. The exclusive strengths and limitations of these two methods are compared with those presented by the frequency-domain Femtosecond Stimulated Raman Scattering (FSRS) technique, highlighting the complementary nature of the three, and the benefits of using them in concert to investigate vibrational dynamics in reactive species.
AB - Pump-impulsive vibrational spectroscopy (pump-IVS) is used to record excited state vibrational dynamics following photoexcitation of two carotenoids, β-carotene and lycopene, with <30 fs temporal resolution, and covering the full vibrational spectrum of the investigated chromophores. The results record the course of S2-S1 internal conversion, followed by vibrational relaxation and decay to the electronic ground state. This interpretation is corroborated by comparison with pump-degenerate-four-wave- mixing (pump-DFWM) experiments on the same systems. The results demonstrate the potential of both time-domain spectroscopic techniques to resolve photochemical dynamics, including fingerprint frequencies which directly reflect changes in bonding and structure in the nascent sample. The exclusive strengths and limitations of these two methods are compared with those presented by the frequency-domain Femtosecond Stimulated Raman Scattering (FSRS) technique, highlighting the complementary nature of the three, and the benefits of using them in concert to investigate vibrational dynamics in reactive species.
UR - http://www.scopus.com/inward/record.url?scp=84881437041&partnerID=8YFLogxK
U2 - 10.1039/c3cp50871d
DO - 10.1039/c3cp50871d
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AN - SCOPUS:84881437041
SN - 1463-9076
VL - 15
SP - 14487
EP - 14501
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 34
ER -