The absorption spectrum of phosphine (PH3) between 2.8 and 3.7 μm: Line positions, intensities, and assignments

Over 8000 line positions and intensities of phosphine (PH3) at 3 μm have been measured at 0.0115 cm−1 resolution with the McMath-Pierce Fourier Transform spectrometer at Kitt Peak. The observed line intensities ranged from 4.13 × 10−6 to 4.69 × 10−2 cm−2 atm−1 at 296 K, for line positions between 2724.477 and 3601.652 cm−1. This region spans eight interacting vibrational states: 3ν2 (2940.8 cm−1), 2ν2 + ν4 (3085.6 cm−1), ν2 + 2ν4 (3214.9 cm−1), ν1 + ν2 (3307.6 cm−1), ν2 + ν3 (3310.5 cm−1), 3ν4 (∼3345 cm−1), ν1 + ν4 (3426.9 cm−1), and ν3 + ν4 (3432.9 cm−1). Assignments have been determined for all the bands except 3ν4 (a weak band in a highly congested area) for a total of 4232 transitions. The total integrated intensity for this region is 5.70 cm−2 atm−1 near 296 K, and assigned lines account for 79% of the observed absorption. The two strongest bands in the region are ν1 + ν4 and ν3 + ν4 with band strengths at 296 K of 1.61 and 2.01 cm−2 atm−1, respectively. An empirical database of PH3 line parameters (positions, intensities, and assignments) is now available. Lower state energies (corresponding to assignments from this study) and line widths from the literature are included; default values are used for unassigned features.