Isotopomer fractionation in the UV photolysis of N(2)O: 3. 3D Ab initio surfaces and anharmonic effects.
The wavelength-dependent isotopic fractionation of N(2)O is calculated, extending our previous work, Parts 1 and 2, in several aspects: (1) the fully three-dimensional ab initio electronic potential and transition dipole moment surfaces of S. Nanbu and M. S. Johnson (J. Chem. Phys. A 2004, 108, 8905) are used to calculate the absorption cross sections, instead of a 2D surface and (2) the vibrational frequencies and wave functions with anharmonicity correction are used for the ground electronic state. The results for the absorption spectrum and for the isotopic fractionation of the different isotopomers are discussed. One difference between experiments measuring the absorption coefficient (von Hessberg et al. Atmos. Chem. Phys. 2004, 4, 1237) and the others that measure instead the photodissociation is also discussed. Experiments on the quantum yield for wavelengths longer than 200 nm (>50 000 cm(-1)) would be helpful in treating the observed difference.
Noyes Laboratory, 127-72, California Institute of Technology, Pasadena, California 91125, and Department of Materials & Life Sciences, Faculty of Science & Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan.
Wei-Chen
WC
Chen
Shinkoh
S
Nanbu
R A
RA
Marcus