Quenching of highly vibrationally excited pyrimidine by collisions with CO{sub 2}
- Department of Chemistry and Biochemistry, Brigham Young University, Provo, Utah 84602 (United States)
Relaxation of highly vibrationally excited pyrimidine (C{sub 4}N{sub 2}H{sub 4}) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E{sup '}=40 635 cm{sup -1}) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58-80) of the 00{sup 0}0 ground state of CO{sub 2} resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO{sub 2} recoil velocity distribution for J=58-80 of the 00{sup 0}0 state. Rate constants and probabilities for collisions populating these CO{sub 2} rotational states were determined. The measured energy transfer probabilities, indexed by final bath state, were resorted as a function of {delta}E to create the energy transfer distribution function, P(E,E{sup '}), from E{sup '}-E{approx}1300-7000 cm{sup -1}. P(E,E{sup '}) is fitted to a single exponential and a biexponential function to determine the average energy transferred in a single collision between pyrimidine and CO{sub 2} and parameters that can be compared to previously studied systems using this technique, pyrazine/CO{sub 2}, C{sub 6}F{sub 6}/CO{sub 2}, and methylpyrazine/CO{sub 2}. P(E,E{sup '}) parameters for these four systems are also compared to various molecular properties of the donor molecules. Finally, P(E,E{sup '}) is analyzed in the context of two models, one which suggests that the shape of P(E,E{sup '}) is primarily determined by the low-frequency out-of-plane donor vibrational modes and one which suggests that the shape of P(E,E{sup '}) can be determined by how the donor molecule final density of states changes with {delta}E.
- OSTI ID:
- 21024744
- Journal Information:
- Journal of Chemical Physics, Vol. 128, Issue 5; Other Information: DOI: 10.1063/1.2825599; (c) 2008 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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