scholarly journals The calculation of TV, VT, VV, VV' − rate coefficients for the collisions of the main atmospheric components

1998 ◽  
Vol 16 (7) ◽  
pp. 838-846 ◽  
Author(s):  
A. S. Kirillov

Abstract. The first-order perturbation approximation is applied to calculate the rate coefficients of vibrational energy transfer in collisions involving vibrationally excited molecules in the absence of non-adiabatic transitions. The factors of molecular attraction, oscillator frequency change, anharmonicity, 3-dimensionality and quasiclassical motion have been taken into account in the approximation. The analytical expressions presented have been normalized on experimental data of VT-relaxation times in N2 and O2 to obtain the steric factors and the extent of repulsive exchange potentials in collisions N2-N2 and O2-O2. The approach was applied to calculate the rate coefficients of vibrational-vibrational energy transfer in the collisions N2-N2, O2-O2 and N2-O2. It is shown that there is good agreement between our calculations and experimental data for all cases of energy transfer considered.Key words. Ionosphere (Auroral ionosphere; ion chemistry and composition). Atmospheric composition and structure (Aciglow and aurora).

1976 ◽  
Vol 31 (10) ◽  
pp. 1203-1209 ◽  
Author(s):  
Willi Janiesch ◽  
Helmut Ulrich ◽  
Peter Hess

Abstract The vibrational relaxation time for pure SiH4 is 0.10, 0.083 and 0.072 μsec atm (±30%) at 295 K, 375 K and 462 K. For SiH4 diluted in He, D2 and H2 the corresponding numbers are 0.16, 0.081 and 0.031 μsec atm (± 30%) at 295 K. The binary two-level theory has been used to deter-mine the four V -R, T rates in the system SiH4 -CH4, and the rate for V-V exchange between SiH4 and CH4 from experimental data. From the Schwartz-Slawsky-Herzfeld-formula for V -T and V -V, T processes an equation is derived describing V -R and V -V, R energy exchange. The different models are compared with experimental data, especially with those found for the system SiH4 -CH4.


Vibrational relaxation times have been measured in CO 2 + H 2 mixtures from 344 to 742 K by a laser-schlieren method. Normal and para hydrogen mixtures have been used. The scatter in the results is small and there is excellent agreement with a recent ultrasonic measurement at room temperature. The results are not in accord with the theoretical calculations of Sharma. They show that both rotational-vibrational and translational-vibrational energy transfer must be important for this case and throw light on the importance of rotational-vibrational energy transfer in other systems.


1992 ◽  
Vol 96 (7) ◽  
pp. 5111-5122 ◽  
Author(s):  
Xueming Yang ◽  
Eun H. Kim ◽  
Alec M. Wodtke

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