Nitrogen dioxide, NO 2 , is a free radical composed of the two most abundant elements in Earth’s atmosphere, nitrogen and oxygen, and is relevant to atmospheric and combustion chemistry. The electronic structure of even its lowest-lying states is remarkably complex, with various conical intersections and Renner–Teller pairings, giving rise to complex and perturbed vibronic states. Here we report some analysis of the 18 molecular states of doublet spin-multiplicity formed by combining ground-state N( 4 S u ) and O( 3 P g ) atoms. In this work, three-dimensional potential energy surfaces were fit at the MRCI(Q)-F12/VTZ-F12 level, describing the lowest four ($\tilde X$, $\tilde A$, $\tilde B$, and $\tilde C$) electronic states. A properties-based diabatization procedure was applied to accommodate the intersections, producing energies in a quasidiabatic representation and yielding couplings that were also fit into surfaces. The low-lying vibrational levels on the ground $\tilde X$ state were computed and compared with experimental measurements. Compared to experiment, the lowest 125 calculated vibrational levels (up to 8500 cm –1 above the zero-point energy) have a root-mean-squared error of 16.5 cm –1 . In addition, dipole moments for each of the lowest four electronic states—and the transition dipoles between them—were also computed and fit. With the coupled energy and dipole surfaces, the electronic spectrum was calculated in absolute intensity and compared with experimental measurements. Detailed structure in the experimental spectrum was successfully reproduced, and the total integrated intensity matches experiment to an accuracy of ~1.5% with no empirical adjustments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1990

The JPL Molecular Contamination Investigation Facility

The Molecular Contamination Investigation Facility (MCIF) is discussed in terms of its use for improving the far-UV performance of a camera and its broader applications. The MCIF incorporates two independent vacuum systems with sample isolation chambers and regulated heat exchangers as well as three quartz-crystal microbalances (QCMs) and a residual gas analyzer. One cryogenic QCM is heat sunk into an LN2 heat exchanger, while the others are thermoelectrically controlled and are heat sunk into a regulated heat exchanger. Outgas accumulation can be measured at three surface temperatures between -180 and 80 C simultaneously, and results are presented for the testing of 34 samples in a large-chambered system and 22 samples in a system with a smaller chamber. The MCIF results provide a database for fabrication processes, material selection, maximum bakeout temperatures, and the development of an ultraclean bakeout chamber.

Taylor, Daniel M.↗