Journal
JOURNAL OF CHEMICAL PHYSICS
Volume 144, Issue 19, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4948629
Keywords
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Funding
- National Science Foundation [CBET-1336105]
- Defense Threat Reduction Agency (DTRA) [HDTRA1-14-1-0008]
- Div Of Chem, Bioeng, Env, & Transp Sys
- Directorate For Engineering [1336105] Funding Source: National Science Foundation
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The ultrafast relaxation pathway of alpha-terpinene was studied by photoionization-photoelectron spectroscopy for a range of excitation conditions. Time-resolved spectra were obtained upon optical excitation with ultrashort laser pulses at 5.56 eV, 4.96 eV, 4.76 eV, and 4.56 eV, followed by ionization with 3.06 eV pulses. The experiments yielded spectra of the initially excited state, which decays with a time constant of 66 fs, independent of the excitation wavelength. We also observed a sequential series of Rydberg peaks, including the s, p, and d states with n = 3-6, which capture the travel times on the ensuing reaction path. There is no statistically significant dependence of the travel time on the excitation energy. A comparison of the time-dependent signals with those of the un-substituted parent molecule, 1,3-cyclohexadiene, shows that the substituents on a-terpinene slow the reaction down by a factor of about 2. Published by AIP Publishing.
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