التفاصيل البيبلوغرافية
العنوان: |
High-resolution infrared spectroscopy of jet cooled trans-deuteroxycarbonyl (trans-DOCO) radical. |
المؤلفون: |
Kortyna, A., Nesbitt, D. J. |
المصدر: |
Journal of Chemical Physics; 5/21/2019, Vol. 150 Issue 19, pN.PAG-N.PAG, 10p, 1 Diagram, 1 Chart, 6 Graphs |
مصطلحات موضوعية: |
INFRARED spectroscopy, SHEAR waves, MILLIMETER waves, DOPPLER broadening, INFRARED absorption, DIPOLE moments |
مستخلص: |
The rovibrational spectrum of jet cooled trans-deuteroxycarbonyl (trans-DOCO) radical has been explored at suppressed-Doppler resolution via direct infrared absorption spectroscopy. The trans-DOCO is produced in a supersonic slit discharge of rare-gas/CO mixture doped with D2O, whereby the OD forms an energized adduct with CO, cooling in the supersonic expansion and stabilizing DOCO in the trans well. Active laser-frequency stabilization and collisional quenching of Doppler broadening along the slit axis yield <10 MHz frequency precision, with the absorbance noise approaching the quantum shot-noise limit. The current high-resolution spectral results are in excellent agreement with recent studies of the trans-DOCO radical by infrared frequency comb spectroscopy under room temperature conditions [Bui et al., Mol. Phys. 116, 3710 (2018)]. Combined with previous microwave/millimeter wave rotational studies, the suppressed-Doppler infrared data permit characterization of the vibrational ground state, improved structural parameters for the OD stretch vibrational level, and trans-DOCO spin-rotation information in both ground and excited vibrational states. Additionally, the infrared data reveal a-type and much weaker b-type contributions to the spectrum, analysis of which yields orientation of the OD stretch transition dipole moment in the body fixed frame. Of dynamical interest is whether the nascent trans-DOCO complex formed in the entrance channel has sufficient time to convert into the cis-DOCO isomer, or whether this is quenched by rapid stabilization into the trans-DOCO well. Ab initio and Rice–Ramsperger–Kassel–Marcus analysis of the intrinsic reaction coordinate for trans-DOCO to cis-DOCO interconversion rates supports the latter scenario, which helps explain the failure of previous high resolution infrared efforts to detect cis-hydroxycarbonyl. [ABSTRACT FROM AUTHOR] |
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