Near Ultraviolet Absorption Spectra of cis and trans Acrolein and Acrolein-d1

1973 ◽  
Vol 51 (11) ◽  
pp. 1170-1175 ◽  
Author(s):  
G. A. Osborne ◽  
D. A. Ramsay

The absorption spectrum of acrolein-d1 (CH2=CH∙CDO) has been studied in the region 3900 to 4400 Å with path lengths and pressures up to 10 m atm and temperatures from 25 to 160 °C. This study provides additional information for the interpretation of the vibrational structure observed in the 3A″–1A′ (trans), 1A″–1A′ (cis), and 3A″–1A′ (cis) systems of acrolein, in addition to new information for acrolein-d1. Most of the features in these spectra are now assigned.

1974 ◽  
Vol 52 (13) ◽  
pp. 2513-2515 ◽  
Author(s):  
R. A. Back ◽  
C. Willis

The near-ultraviolet absorption spectrum of diimide in liquid ammonia at −50 °C is shifted about 500 Å to the red compared with the gas-phase spectrum, with λmax = 4000 Å. The spectrum is also broadened and the vibrational structure largely obscured. It is suggested that hydrogen bonding is responsible for these changes.Diimide is much more stable in liquid ammonia between −65 and −38 °C than in the gas phase at room temperature. A first-order decay is observed with Arrhenius parameters of A = 1.9 × 103 s−1 and E = 6.6 kcal/mol; this is always preceded by a more rapid, higher-order initial decay which may be related to the rapid decomposition observed during vaporization.


1974 ◽  
Vol 52 (6) ◽  
pp. 1006-1012 ◽  
Author(s):  
R. A. Back ◽  
C. Willis ◽  
D. A. Ramsay

Absorption spectra of N2H2 and N2D2 in the gas phase have been obtained in the region 3000–4300 Å, consisting of about 30 diffuse bands for each compound. Long progressions in the spectra are attributed to excitation of the H—N=N bending mode, v2′, in the upper state, with much shorter progressions arising from the N=N stretching mode, v3′; values of v2′ = 1215 and 910 cm−1 and v3′ = 1550 and 1440 cm−1 were estimated for N2H2 and N2D2 respectively.The spectra are attributed to the 1Bg ← 1Ag(π* ← n+) transition of trans diimide, probably made allowed by vibronic interaction. From Franck–Condon calculations the H—N=N angle in the upper state was estimated to be 132 ± 2°, an increase of 25° from the ground-state value; the increase in the N=N bond length was estimated to be about 0.05 Å.


1968 ◽  
Vol 22 (6) ◽  
pp. 785-786 ◽  
Author(s):  
David N. Bailey ◽  
David K. Roe ◽  
David M. Hercules

1975 ◽  
Vol 53 (21) ◽  
pp. 3269-3275 ◽  
Author(s):  
C. Rullière ◽  
E. C. Colson ◽  
P. C. Roberge

The triplet–triplet (T–T) absorption spectrum of 1,3,6,8-tetraphenylpyrene (TPP) was measured from 400 to 620 nm. The data obtained are compared with theoretical calculations using the Ruedenberg–Scherr FEMO model. A planar triplet state is evidenced by fine vibrational structure. The T–T quenching rate constant measured (1.3 ± 0.1 × 109 M−1 s−1) is 20% of the expected diffusion-controlled value.


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