Appearance potentials of CnH2n+2N+ ions (n = 1-3)

Abstract

MLCT state is higher in energy than remote. For all other complexes eq 6 is employed. For all 423-type complexes, the DQ2+ 2+/1+ reduction potential is -0.65 V, as shown in Table I. Once values of AG are known, estimation of k,, follows easily, using eq 11, with C = -104 mV, and b = -2022 mV. Estimates presented in this Appendix are listed in Table 111.(R~(bpy)~(42n-DQ~+))~+ Series. The onset of emission in the complex Ru(bpy)2(DMB)Z+ is 2.20 eV (Table IV), and the Ru 3+/2+ potential for R~( b p y )~( 4 2 3 -D Q~+ ) is +1.24 V ( Table I) .Equation 7 thus yields a value of 1.24 -2.20 = -0.96 V for the Ru 2+*/3+ potential in R u ( b p~)~( 4 2 3 -D Q~+ ) .With values of -0.65 V for the DQz+ 2+/1+ potential, and 0.05 V (50 mV) for E A R , eq 8 yields an estimate of AG equal to -0.96 + 0.65 -0.05 = -0.36 V or -360 mV. For R~( b p y )~( 4 2 2 -D Q~+ ) and Ru-( b p~)~( 4 2 4 -D Q~+ ) , DQ2+ 2+/1+ potentials (Table I) are -0.44 and -0.77 V, respectively, yielding respective AG estimates (Table 111) of -240 and -570 mV. For these complexes, k,, values are estimated as kr(obsd)/a(calcd), (a = 0.064). These ke-I estimates are found in Table 111.(4) Radecki, B. D.; Allison, J.

Calculation of the Ionization Energies of the Amidogen and Methyl-Substituted Amidogen Radicals: NH2, CH3NH, and CH3NCH3

“…G1 and G2 levels of theory were then used to calculate the ionization energies of the MMA and DMA species, and these were found to disagree to an enormous extent with those from the most recent compilation. However, the values were in close agreement with the values derived from a later experiment by Castleman and co-workers …”

“…Later, Fisher and Henderson 23 looked at mass spectra from a number of compounds and deduced the ionization energy of CH 3 NCH 3 to be e9.42 ( 0.1 eV. As noted above, Castleman and co-workers 9 obtain bounds on the ionization energy of DMA of 9.2 and 9.9 eV. It is perhaps worth adding that there are a number of structural isomers with the empirical formula C 2 H 6 N + .…”

“…Recent mass spectrometric results from Castleman's group have bracketed the appearance potentials (AP) of CH 4 N + and C 2 H 6 N + by looking at reactions of metal ions with suitable alkylamines. The values they obtained were 9.9 ± 0.1 eV ≤ AP(CH 4 N + ) ≤ 10.6 ± 0.1 eV and 9.2 ± 0.2 eV ≤ AP(C 2 H 6 N + ) ≤ 9.9 ± 0.1 eV.…”

Characterization of nitrogen-containing radical products from the photodissociation of trimethylamine using photoionization detection

“…Castleman and co-workers 40 reported a lower (9.2 Ϯ0.2 eV) and upper (9.9Ϯ0.2 eV) limit to the appearance energy of the fragmentation process:…”

The Electronic Structure of the (CH3)2N Radical and the Pyrolysis Mechanism of Dimethylnitrosamine: A HeI Photoelectron Spectroscopic Study

“…Much work has been performed to try to establish the first ionization energy of the simplest members of alkylamidogen group. But the disagreement in the first ionization energy calculated for (CH 3 ) 2 N radical (DMA) is very clear, − and there is no experimental report on ionization energies of different orbitals for the (CH 3 ) 2 N radical until now.…”