ON THE ELECTRONIC-STRUCTURE ASPECTS OF SPIN-FORBIDDEN PROCESSES IN N2O

被引:47
作者
CHANG, AHH
YARKONY, DR
机构
[1] Department of Chemistry, Johns Hopkins University, Baltimore
关键词
D O I
10.1063/1.465826
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
The crossing surfaces corresponding to the intersection of the lowest singlet surface of N2O and the three triplet surfaces correlating with N2 + O(3P) are studied using multireference configuration interaction wave functions comprised principally of 300 000-500 000 terms, but with some calculations using expansions as large as 1 700 000 terms. These (1 1A', 1 3A'), (1 1A', 1 3A''), and (1 1A', 2 3A'') crossing surfaces are characterized in the vicinity of their minimum energy points. The minimum energy crossing structures are each linear and correspond to (X 1SIGMA+, 3PI) and (X 1SIGMA+, 3SIGMA-) intersections. The minimum energy point on (X 1SIGMA+, 3PI) crossing surface, was found to be approximately 58 kcal/mol above the N2O(X 1SIGMA+) minimum. The minimum energy point on (X 1SIGMA+, 3SIGMA-) crossing surface was found to be 71 kcal/mol above the N2O(X 1SIGMA+) minimum. The N-N bond distance is similar at the (X 1SIGMA+, 3PI) and (X 1SIGMA+, 3SIGMA-) minimum energy crossing structures, being 1.116 and 1. 113 angstrom, respectively, and approximately equal to that in isolated N2(X 1SIGMA(g)+). The N-O bond is 1.72 and 1.96 angstrom for the (X 1SIGMA+, 3PI) and (X 1SIGMA+, 3SIGMA-) minimum energy crossing structures, respectively, and significantly stretched when compared with its value, 1.18 angstrom, at the equilibrium geometry of N2O(X 1SIGMA+). The spin-orbit couplings were also evaluated on each of the (1 1A',1 3A'), (1 1A', 1 3A''), and (1 1A', 2 3A'') crossing surfaces. The (X 1SIGMA+, 3PI) and (X 1SIGMA+, 3SIGMA-) spin-orbit interactions were found to be approximately 90 and approximately 9 cm-1 at their respective minimum energy crossing structures. The crossing surfaces persist in the vicinity of the minimum energy crossing points. However for increased deviations from collinearity avoided crossings are found.
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页码:6824 / 6831
页数:8
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