We have recently determined the induced dipole surface (IDS) and potential energy surface (PES) of collisional H2-He complexes. We have used these surfaces to compute the binary collision-induced absorption spectra of H2 molecules interacting with He atoms and of D2 molecules interacting with He atoms. Here we extend these calculations to the case of T2 molecules interacting with He atoms. Whereas the electronic structure of X2-He is virtually the same for all hydrogen isotopes X = H, D, or T, the collisional dynamics and molecular scattering wave functions are different for the different collisional pairs. We have calculated spectra up to a temperature of 9000?K and frequencies up to 20,000?cm?1. Here we compare the calculated collision-induced absorption spectra for the different hydrogen isotopes. While we have observed reasonable agreement between our calculations and laboratory measurements for the collisional H2-He and D2-He complexes, there are no laboratory measurements for T2-He collisional complexes, and one must rely on the fundamental theory, supported by the agreement between theory and experiment for the other isotopes. It is an interesting fact that even the so-called infrared-inactive gases, such as hydrogen and its homonuclear isotopes, absorb infrared radiation, if sufficiently high gas densities are encountered [1–4]. This absorption can be traced back to transient electric dipole moments that are induced during collisions of two or more molecules by the same mechanisms that result in the intermolecular forces, that is, by exchange, dispersion forces, and multipolar induction. Modulation of these induced dipole moments due to vibration, rotation, and relative translational motion leads to collision-induced absorption (CIA) of radiation from applied electromagnetic fields. Collision-induced absorption is omnipresent in dense media—it has been observed in dense gases, liquids, and solids [1, 5, 6]. Laboratory measurements of CIA are performed at a very limited range of selected temperatures and frequencies. In contrast to that, the fundamental theory [1] makes it possible to compute collision-induced absorption spectra reliably, over a wide range of temperatures and frequencies, thereby providing numerical values for the absorption intensities even where laboratory measurements do not exist. To compute the binary collision-induced absorption spectra from the fundamental theory, the induced dipole surfaces (IDSs) and potential energy surfaces (PESs) of the binary van der Waals complexes under consideration have to be known. These
References
[1]
L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, New York, NY, USA, 2006.
[2]
W. Meyer and L. Frommhold, “Collision-induced rototranslational spectra of H2-He from an accurate ab initio dipole moment surface,” Physical Review A, vol. 34, no. 4, pp. 2771–2779, 1986.
[3]
L. Frommhold and W. Meyer, “Erratum: Collision-induced rotovibrational spectra of H2-He pairs from first principles,” Physical Review A, vol. 35, no. 2, pp. 632–638, 1987.
[4]
L. Frommhold and W. Meyer, “Collision-induced rotovibrational spectra of H2-He pairs from first principles,” Physical Review A, vol. 41, no. 1, p. 534, 1990.
[5]
G. Birnbaum, Phenomena induced by intermolecular interactions, NATO Advanced Research Workshop Series B127, Plenum Press, New York, NY, USA, 1985.
[6]
G. C. Tabisz and M. N. Neuman, Collision- and Interaction-Induced Spectroscopy, Series C, vol. 452 of NATO Science Series C: Mathematical and Physical Sciences, Kluwer Academic, Dodrecht, The Netherlands, 1st edition, 1995.
[7]
L. Frommhold, M. Abel, F. Wang, M. Gustafsson, X. Li, and K. L. C. Hunt, “Infrared atmospheric emission and absorption by simple molecular complexes, from first principles,” Molecular Physics, vol. 108, no. 17, pp. 2265–2272, 2010.
[8]
X. Li, A. Mandal, E. Miliordos, and K. L. C. Hunt, “Interaction-induced dipoles of hydrogen molecules colliding with helium atoms: A new ab initio dipole surface for high-temperature applications,” Journal of Chemical Physics. In press.
[9]
M. Abel, L. Frommhold, X. Li, and K. L.C. Hunt, “Note: computation of collision-induced absorption by dense deuterium-helium gas mixtures,” Journal of Chemical Physics, vol. 134, no. 7, 2011.
[10]
M. Abel and L. Frommhold, “Note: collision-induced infrared absorption by gaseous deuterium,” Journal of Chemical Physics, vol. 133, no. 14, Article ID 146101, 2 pages, 2010.
[11]
M. Gustafsson, L. Frommhold, and W. Meyer, “Infrared absorption spectra by H2-He collisional complexes: the effect of the anisotropy of the interaction potential,” Journal of Chemical Physics, vol. 113, no. 9, pp. 3641–3650, 2000.
[12]
F. A. Gianturco, T. González-Lezana, G. Delgado-Barrio, and P. Villarreal, “The binding of 4He and 3He to a hydrogen molecule: a computational study for pH2 and oH2,” Journal of Chemical Physics, vol. 122, no. 8, Article ID 084308, 5 pages, 2005.
[13]
A. Kalinin, O. Kornilov, L. Y. Rusin, and J. P. Toennies, “Evidence for a bound HeH2 halo molecule by diffraction from a transmission grating,” Journal of Chemical Physics, vol. 121, no. 2, pp. 625–627, 2004.
[14]
A. I. Boothroyd, P. G. Martin, and M. R. Peterson, “Accurate analytic He-H2 potential energy surface from a greatly expanded set of ab initio energies,” Journal of Chemical Physics, vol. 119, no. 6, pp. 3187–3207, 2003.