Anomalous Intensities in the 2+1 REMPI Spectrum of the E 1Π–X 1Σ+ Transition of CO

Gunthardt, C. E.; Wallace, C. J.; Hall, G. E.; Field, R. W.; North, S. W.

doi:10.1021/acs.jpca.9b00109

Title: Anomalous Intensities in the 2+1 REMPI Spectrum of the E ¹Π–X ¹Σ⁺ Transition of CO

Journal Article · Wed Feb 27 00:00:00 EST 2019 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.9b00109· OSTI ID:1498862

Gunthardt, C. E. ^[1]; Wallace, C. J. ^[1];

^[2];

^[3];

^[1]

Texas A & M Univ., College Station, TX (United States). Dept. of Chemistry
Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemistry

We report here on one-color experiments near 214 nm involving the photodissociation of jet-cooled OCS to produce high rotational states (40 < J < 80) of CO (X ¹Σ⁺, v = 0, 1) which were then ionized by 2+1 resonance-enhanced multiphoton ionization via the E ¹Π state. The nominally forbidden Q-branch of the two-photon E ¹Π–X ¹Σ⁺ transition is observed with intensity comparable to the allowed R-branch. The bright character of the high-J Q-branch lines can be described quantitatively as intensity borrowing due to mixing of the E ¹Π and C ¹Σ⁺ states, using J-dependent mixing coefficients extrapolated from the observed Λ-doubling in the lower rotational levels of the E state. In addition to the significant enhancement of Q-branch intensities above the values predicted by conventional two-photon line strengths for a ¹Π–¹Σ⁺ transition, the high-J lines of the R- and P-branches appear to be suppressed in intensity by approximately a factor of 3 compared to the unperturbed low-J line strengths, most likely due to perturbations associated with a ¹Σ^– state. The E-state rotational term values for J < 80, v = 0 derived from the present spectra agree within our measurement and calibration uncertainties with the extrapolations based on the molecular constants previously derived from rotational levels with J < 50. The E–X transition is attractive for future application to photodissociation dynamics and rotational polarization measurements of CO photofragments, with convenient access to state-selective probing on multiple rotational branches, which exhibit different sensitivity to fragment alignment.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States); Texas A & M Univ., College Station, TX (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Robert A. Welch Foundation (United States); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704; A-1405; CHE-1800410

OSTI ID:: 1498862

Report Number(s):: BNL-211352-2019-JAAM

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 123, Issue 13; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Anomalous Intensities in the 2+1 REMPI Spectrum of the E ¹Π–X ¹Σ⁺ Transition of CO