Issue 0, 1975

Vibrational excitation of N2 by the spin-orbit relaxation of Hg(63P1→ 63P0)

Abstract

The lifetime of Hg(63P0) in a gas mixture of Ar + N2 at room temperature was measured by a phase-shift method. A mixture containing a trace of Hg vapour was illuminated by 253.7 nm radiation, whose intensity was modulated at a frequency in the range of 120–1000 Hz, and the resulting a.c. component of Hg(63P0) concentration was monitored by a lock-in system. The lifetime is inversely proportional to the square root of the 253.7 nm radiation intensity. This is attributable to accumulation of N2 in the v= 1 level through the spin-orbit relaxation Hg(63P1)+ N2(v= 0)→ Hg(63P0)+ N2(v= 1), and the reverse of this reaction results in shortening of the lifetime. The accumulation of N2 in the v= 1 level is due to the fact that N2(v= 1) is deactivated by a factor of about 102 less efficiently than Hg(63P0). The observed dependence of the lifetime on the 253.7 nm intensity made it possible to deduce the rate constant of the relaxation. The result agreed with the value determined from the lifetime measurement of Hg(63P1) in N2. Thus, it is concluded that the spin-orbit relaxation of Hg(63P1) in N2 consists of the electronic-to-vibrational energy transfer. The reciprocal lifetime of N2(v= 1) was determined to be 1.2 ± 0.3 s–1 in the mixture of 1 Torr N2+ 9 Torr Ar. This leads to the estimate that the collision probability for deactivation of N2(v= 1) on the wall of a quartz cell is 1 × 10–4.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans. 2, 1975,71, 1164-1172

Vibrational excitation of N2 by the spin-orbit relaxation of Hg(63P1→ 63P0)

H. Horiguchi and S. Tsuchiya, J. Chem. Soc., Faraday Trans. 2, 1975, 71, 1164 DOI: 10.1039/F29757101164

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Spotlight

Advertisements