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Optical Spectroscopic Determination of the Zero-Field Splitting in Vibronic Levels of the Triplet State of Nitrite

Hochstrasser, Robin M. and Zewail, Ahmed H. (1971) Optical Spectroscopic Determination of the Zero-Field Splitting in Vibronic Levels of the Triplet State of Nitrite. Journal of Chemical Physics, 54 (7). pp. 2979-2981. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:HOCjcp71a

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Abstract

We have used conventional high resolution optical spectroscopic methods to determine the principal values of the fine structure tensor for the lowest triplet state (3B1 at 18 959 cm^−1) of NO<sub>2</sub><sup> - </sup> in Na NO2 single crystals. From the intensities in the Zeeman spectrum we find [dformula D - E = 0.86 [plus-minus] 0.04cm[sup -1],] [dformula D + E = 0.40 [plus-minus] 0.04cm[sup -1],] where the z axis is taken as the twofold axis and E = (Z − X) / 2. From the measurement of line positions in the high-field Zeeman spectrum we find D − E = 0.84 ± 0.05cm−1,D + E = 0.41 ± 0.05cm−1. The values of D and E calculated for one-center spin–spin interaction are D − E = 0.42cm^−1 and D + E = 0.24cm^−1. The calculated ordering of the spin states is the same as that observed, but we suggest that there is significant second-order spin–orbit energy associated with the real splittings. Roughly the same splittings are seen for different vibronic levels of 3B1 associated with nu2[prime]


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1063/1.1675282DOIUNSPECIFIED
http://link.aip.org/link/?JCPSA6/54/2979/1PublisherUNSPECIFIED
Additional Information:© 1971 American Institute of Physics. Received 19 October 1970. This research was supported in part by a U.S. Department of Health Grant, G.M. 12592, and in part by the Advanced Research Projects Agency.
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National Institutes of HealthGM 12592
Advanced Research Projects AgencyUNSPECIFIED
Record Number:CaltechAUTHORS:HOCjcp71a
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:HOCjcp71a
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Deposited On:11 Jan 2009 07:30
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