INTERNAL ENERGY-DISTRIBUTIONS FROM NITROGEN-DIOXIDE FLUORESCENCE .2. COLLISIONAL ENERGY-TRANSFER FROM EXCITED NITROGEN-DIOXIDE

被引:11
作者
PATTEN, KO
JOHNSTON, HS
机构
[1] UNIV CALIF BERKELEY,DEPT CHEM,BERKELEY,CA 94720
[2] LAWRENCE BERKELEY LAB,DIV CHEM SCI,BERKELEY,CA 94720
关键词
D O I
10.1021/j100141a005
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
We follow the collisional deactivation of laser-excited nitrogen dioxide through its dispersed fluorescence. The energy acceptor gases are NO2 at four excitation energies ranging from 18 828 to 24 989 cm-1 and five monatomic gases, four diatomic gases, and three polyatomic gases with 18 828-cm-1 excitation energy. The nominal products are the shapes of the internal energy distributions, which are obtained and plotted for several representative cases. From these distributions, the first three moments of the internal energy distributions are derived as a function of molecular collisions and tabulated as (i) the average internal energy, (ii) energy spread, and (iii) skewness. These quantities are plotted against c(M)t, the product of buffer gas concentration c(M) and delay time after laser excitation t(0.5-2 mus), which is a quantity proportional to number of collisions. The negative slope of average energy vs c(M)t is the macroscopic energy-transfer rate constant, k(E)(M). Average energies [E] for all NO2-buffered data taken at four excitation wavelengths are well represented by the single equation, fourth order in energy: d[E]/d(c(NO2)t) = -k4[E]4, where k4 = 8.06 X 10(-25) (CM3)energy molecule-1 cm3 s-1. Energy-transfer rates increase in the order monatomics, diatomics, and polyatomics. The energy-transfer rate constants are in reasonable agreement with most values reported in the literature. Second and third moments of the internal energy population of collisionally deactivated nitrogen dioxide are the novel products of this article and show interesting trends with the number of Lennard-Jones collisions.
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页码:9904 / 9915
页数:12
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