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The absorption spectrum of D2: Ultrasensitive cavity ring down spectroscopy of the (2-0) band near 1.7 μm and accurate ab initio line list up to 24 000 cm-1.
- Source :
-
Journal of Chemical Physics . 5/14/2012, Vol. 136 Issue 18, p184309. 10p. 3 Charts, 7 Graphs. - Publication Year :
- 2012
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Abstract
- Eleven very weak electric quadrupole transitions Q(2), Q(1), S(0)-S(8) of the first overtone band of D2 have been measured by very high sensitivity CW-cavity ring down spectroscopy (CRDS) between 5850 and 6720 cm-1. The noise equivalent absorption of the recordings is on the order of αmin ≈ 3 × 10-11 cm-1. By averaging a high number of spectra, the noise level was lowered to αmin ≈ 4 × 10-12 cm-1 in order to detect the S(8) transition which is among the weakest transitions ever detected in laboratory experiments (line intensity on the order of 1.8 × 10-31 cm/molecule at 296 K). A Galatry profile was used to reproduce the measured line shape and derive the line strengths. The pressure shift and position at zero pressure limit were determined from recordings with pressures ranging between 10 and 750 Torr. A highly accurate theoretical line list was constructed for pure D2 at 296 K. The intensity threshold was fixed to a value of 1 × 10-34 cm/molecule at 296 K. The obtained line list is provided as supplementary material. It extends up to 24 000 cm-1 and includes 201 transitions belonging to ten v-0 cold bands (v = 0-9) and three v-1 hot bands (v = 1-3). The energy levels include the relativistic and quantum electrodynamic corrections as well as the effects of the finite nuclear mass. The quadrupole transition moments are calculated using highly accurate adiabatic wave functions. The CRDS line positions and intensities of the first overtone band are compared to the corresponding calculated values and to previous measurements of the S(0)-S(3) lines. The agreement between the CRDS and theoretical results is found within the claimed experimental uncertainties (on the order of 1 × 10-3 cm-1 and 2% for the positions and intensities, respectively) while the previous S(0)-S(3) measurements showed important deviations for the line intensities. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 136
- Issue :
- 18
- Database :
- Academic Search Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 75230789
- Full Text :
- https://doi.org/10.1063/1.4707708