Abstract
The A {sup 1}A{double prime} {l arrow} X {sup 1}A{prime} absorption spectrum of gaseous nitrous acid has been measured in the 300-400-nm range. Absolute cross sections were determined by a combination of gas-phase and wet chemical analysis. The cross sections of prominent bands are 25% larger than the recommended values of Stockwell and Calvert. The influence of spectral resolution on absolute and differential absorption cross sections was also investigated. The integrated band area of the n{pi}* transition yields an oscillator strength f = (8.90 {plus minus} 0.36) {times} 10{sup {minus}4}, less than the reported liquid phase value of 2 {times} 10{sup {minus}3}. The equilibrium constant K = p{sub trans}/p{sub cis}, based on the assumption that the oscillator strength of the n{pi}* transition is the same for both rotamers, was found to be 3.25 {plus minus} 0.30 at 277 K. This yields an energy difference {Delta}E between trans- and cis-HONO of -2,700 J mol{sup {minus}1} in the electronic ground state, and -6,000 J mol{sup {minus}1} in the excited state.
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