Philosophical Transactions A H2O−N2 collision-induced absorption band intensity in the region of the N2 fundamental: ab initio investigation of its temperature dependence and comparison with laboratory data by Yu. I. Baranov, I. A. Buryak, S. E. Lokshtanov, V. A. Lukyanchenko, and A. A. Vigasin Philosophical Transactions A Volume 370(1968):2691-2709 June 13, 2012 ©2012 by The Royal Society

Notation of intermolecular coordinates. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

Radial dependence of the potential energy in geometry: ϕ=0°, θ1=45°, ψ=0°, θ2=0° (close to global minimum) calculated with CCSD(T) method using aug-cc-pV(D,T)Z (light and dark grey lines) basis sets and extrapolation to CBS (black solid line) limit. Radial dependence of the potential energy in geometry: ϕ=0°, θ1=45°, ψ=0°, θ2=0° (close to global minimum) calculated with CCSD(T) method using aug-cc-pV(D,T)Z (light and dark grey lines) basis sets and extrapolation to CBS (black solid line) limit. The CBS extrapolated results of Tulegenov et al. [6] (black dashed line) with the use of SP-aug-cc-pVXZ basis set are shown for comparison. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

H2O−N2 second cross virial coefficient obtained in our calculations and in Tulegenov et al. [6] compared with experimental data (triangles). H2O−N2 second cross virial coefficient obtained in our calculations and in Tulegenov et al. [6] compared with experimental data (triangles). The experimental data points are taken from table 4 of Tulegenov et al. [6] (dashed line) where appropriate referencing can be found. Solid line represents our results obtained with CCSD(T) PES. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

Radial dependence of the H2O−N2 induced dipole (as calculated at aug-cc-pVTZ CCSD(T) level, heavier lines) at representative angular geometries and three values of N−N bond length. Radial dependence of the H2O−N2 induced dipole (as calculated at aug-cc-pVTZ CCSD(T) level, heavier lines) at representative angular geometries and three values of N−N bond length. Lighter lines show the result of electrostatic evaluation of the dipole. Solid lines relate to stretched and compressed N−N bonds in a nitrogen molecule, dashed lines stand for equilibrium N−N length in N2 molecule. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

Water vapour–nitrogen continuum profile at 352 K (heavier line) and the MT_CKD model (grey line). Water vapour–nitrogen continuum profile at 352 K (heavier line) and the MT_CKD model (grey line). Watkins et al. [21] data (relating to 298 K) are shown by grey circles and Burch & Ault [22] data (relating to 296 K) are shown by black squares. Dashed lines show extrapolated background absorption owing to neighbouring H2O−N2 continuum bands. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

The residual absorption profile (ΔCf=Cf – background; see figure 5) showing the N2 collision-induced absorption fundamental band induced by H2O. The residual absorption profile (ΔCf=Cf – background; see figure 5) showing the N2 collision-induced absorption fundamental band induced by H2O. Induced band profile is contaminated mostly in the wing by HDO and, presumably, CO2 extra absorptions (shaded areas). Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

Temperature variations of the integrated intensity of the N2 fundamental band induced by interaction with H2O. Temperature variations of the integrated intensity of the N2 fundamental band induced by interaction with H2O. Our best estimate refers to CCSD(T) method with extrapolation to CBS. Experimental data obtained in this work are shown by solid circles. The calculated point from Brown & Tipping [7] was found by approximate integration from the published graph. Solid curve, CCSD(T); dashed curve, using PES from Tulegenov et al. [6]; dot-dashed curve, MP2; filled circles, experimental; open circle, calculated from Brown & Tipping [7]. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

Temperature variations of the integrated intensity of the N2 collision-induced fundamental in pure nitrogen (from Lokshtanov et al. [11], theoretical curve is slightly corrected after renewed integration procedure, experimental points refer to earlier studi... Temperature variations of the integrated intensity of the N2 collision-induced fundamental in pure nitrogen (from Lokshtanov et al. [11], theoretical curve is slightly corrected after renewed integration procedure, experimental points refer to earlier studies [9,28,29]). Solid line denotes calculated variation; squares, triangles, and circles denote observed variation. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society

Frequency shift in N2 perturbed by H2O (a) and effective rotational constant of H2O−N2 pairs (b) averaged over thermally excited ensemble. Frequency shift in N2 perturbed by H2O (a) and effective rotational constant of H2O−N2 pairs (b) averaged over thermally excited ensemble. Solid line denotes present work; circle denotes experimental work of Leung et al. [1]. Yu. I. Baranov et al. Phil. Trans. R. Soc. A 2012;370:2691-2709 ©2012 by The Royal Society