Thomas A. A. Oliver, Graeme A. King, Michael N. R. Ashfold

Transcription

1 Electronic Supplementary Information for: Position Matters: Competing O H and N H Photodissociation Pathways in Hydroxy- and Methoxy- substituted Indoles Thomas A. A. Oliver, Graeme A. King, Michael N. R. Ashfold 1. Photoionisation Mass Spectrometry (a) 4-HI Ion TOF mass spectra obtained following excitation of jet cooled 4-HI at λ phot = (a) nm, (b) nm with Lyman-α radiation (c) nm and Lyman-α radiation. (b) 5-HI Ion TOF mass spectra obtained following excitation of jet cooled 5-HI at λ phot = (a) nm, (b) nm and Lyman-α. 1

2 (c) 4-MI Ion TOF mass spectrum obtained following excitation of jet cooled 4-MI at λ phot = nm. (d) 5-MI Ion TOF mass spectrum obtained following excitation of jet cooled 5-MI at λ phot = nm. 2

3 2. Resonance Enhanced Multiphoton Absorption Spectroscopy (a) 5-HI REMPI excitation spectrum of 5-HI between nm > λ > nm, with the 1 L b -S 0 origin features for both conformers indicated. (b) 5-MI REMPI excitation spectrum of jet-cooled 5-MI molecules between nm > λ > nm. 3

4 3. H(Rydberg) Atom Photofragment Translational Spectroscopy E int spectrum resulting from the photodissociation of the 4-HI (gauche) conformer at λ phot = nm. 4

5 4. Baseline subtraction of 4-MI E int spectra at λ phot = and nm The underlying featureless background was fitted to the side of a gaussian and subtracted from the respective raw E int spectrum (see main paper fig. 12). The peaks at E int = 0 cm -1 and 220 cm -1 were then each fitted to a gaussian, allowing us to deduce the relative integrated areas for λ phot = (a) nm and (b) nm. The ratio of the E int = 0 cm -1 /E int = 220 cm -1 peaks was deduced for (a) to be 1.2:1 and (b) 1.4:1. The peak intensities, however, show a marked difference in ratios: (a) = 1.69:1 and (b) 2.7:1. 5

6 5. Calculated normal mode wavenumbers (a) 4-HI and 4-HI-Oyl and 4-HI-Nyl radical products 4-HI ( X ~ 1 A ) 4-HI-Oyl ( X ~ 2 A ) 4-HI-Nyl ( X ~ 2 A ) Mode Sym. Harm. Anharm. Mode Sym. Harm. Anharm. Mode Sym. Harm. Anharm. ν 1 a' Disappearing Mode ν 1 a' ν 2 a' ν 1 a' Disappearing Mode ν 3 a' ν 2 a' ν 2 a' ν 4 a' ν 3 a' ν 4 a' ν 5 a' ν 4 a' ν 3 a' ν 6 a' ν 5 a' ν 5 a' ν 7 a' ν 6 a' ν 6 a' ν 8 a' ν 7 a' ν 8 a' ν 9 a' ν 8 a' ν 7 a' ν 10 a' ν 10 a' ν 10 a' ν 11 a' ν 9 a' ν 9 a' ν 12 a' ν 13 a' ν 11 a' ν 13 a' ν 11 a' Disappearing Mode ν 14 a' ν 12 a' ν 13 a' ν 15 a' ν 14 a' ν 12 a' ν 16 a' Disappearing Mode ν 14 a' ν 17 a' ν 15 a' ν 15 a' ν 18 a' ν 16 a' ν 16 a' ν 19 a' ν 17 a' ν 17 a' ν 20 a' ν 18 a' ν 18 a' ν 21 a' ν 19 a' ν 19 a' ν 22 a' ν 20 a' ν 22 a' ν 23 a' ν 21 a' ν 20 a' ν 24 a' ν 22 a' ν 21 a' ν 25 a' ν 23 a' ν 23 a' ν 26 a' ν 24 a' ν 24 a' ν 27 a' ν 25 a' ν 25 a' ν 28 a' ν 26 a' ν 26 a' ν 29 a' ν 27 a' ν 27 a' ν 30 a' ν 28 a' ν 28 a' ν 31 a' ν 29 a' ν 29 a' ν 32 a'' ν 30 a'' ν 30 a'' ν 33 a'' ν 31 a'' ν 31 a'' ν 34 a'' ν 32 a'' ν 32 a'' ν 35 a'' ν 33 a'' ν 33 a'' ν 36 a'' ν 35 a'' ν 35 a'' ν 37 a'' ν 34 a'' ν 34 a'' ν 38 a'' ν 36 a'' ν 36 a'' ν 39 a'' ν 37 a'' ν 37 a'' ν 40 a'' ν 38 a'' ν 38 a'' ν 41 a'' ν 39 a'' Disappearing Mode ν 42 a'' Disappearing Mode ν 39 a'' ν 43 a'' ν 40 a'' ν 40 a'' ν 44 a'' ν 41 a'' ν 41 a'' ν 45 a'' ν 42 a'' ν 42 a'' Calculated harmonic (harm.) and anharmonically (anharm.) corrected vibrational wavenumbers (in cm -1 ) at the DFT/B3LYP/6-311+G** level for 4-HI and the corresponding radicals arising from O H (4-HI-Oyl) or N H (4-HI-Nyl) bond fission. The parent modes are labelled according to Herzberg notation i, whereas the ordering of radical modes has been adjusted so as to map through from those of the parent molecule. 6

7 (b) 4-MI and 4-MI-Nyl 4-MI( X ~ 1 A ) 4-MI-Nyl( X ~ 2 A ) Mode Sym. Harm. Anharm. Mode Sym. Harm. Anharm. ν 1 a' Disappearing Mode ν 2 a' ν 1 a' ν 3 a' ν 4 a' ν 4 a' ν 2 a' ν 5 a' ν 3 a' ν 6 a' ν 5 a' ν 7 a' ν 6 a' ν 8 a' ν 7 a' ν 9 a' ν 9 a' ν 10 a' ν 8 a' ν 11 a' ν 10 a' ν 12 a' ν 12 a' ν 13 a' ν 11 a' ν 14 a' ν 13 a' ν 15 a' ν 14 a' ν 16 a' Disappearing Mode ν 17 a' ν 16 a' ν 18 a' ν 15 a' ν 19 a' ν 17 a' ν 20 a' ν 18 a' ν 21 a' ν 19 a' ν 22 a' ν 20 a' ν 23 a' ν 22 a' ν 24 a' ν 21 a' ν 25 a' ν 23 a' ν 26 a' ν 24 a' ν 27 a' ν 25 a' ν 28 a' ν 26 a' ν 29 a' ν 27 a' ν 30 a' ν 28 a' ν 31 a' ν 29 a' ν 32 a' ν 30 a' ν 33 a' ν 31 a' ν 34 a' ν 32 a' ν 35 a' ν 33 a' ν 36 a' ν 34 a' ν 37 a'' ν 35 a'' ν 38 a'' ν 36 a'' ν 39 a'' ν 37 a'' ν 40 a'' ν 38 a'' ν 41 a'' ν 39 a'' ν 42 a'' ν 40 a'' ν 43 a'' ν 41 a'' ν 44 a'' ν 43 a'' ν 45 a'' ν 42 a'' ν 46 a'' ν 44 a'' ν 47 a'' ν 45 a'' ν 48 a'' ν 46 a'' ν 49 a'' Disappearing Mode ν 50 a'' ν 47 a'' ν 51 a'' ν 49 a'' ν 52 a'' ν 48 a'' ν 53 a'' ν 50 a'' ν 54 a'' ν 51 a'' Calculated harm. and anharm. corrected vibrational wavenumbers (in cm -1 ) at the DFT/B3LYP/6-311+G** level for 4-MI and the corresponding 4-MI-Nyl radical. Again labelled according to Herzberg notation i, and the ordering of radical modes has been adjusted so as to map through from those of the parent molecule. i G. Herzberg, Infrared and Raman Spectra of Polyatomic Molecules; van Nostrand: Princeton, NJ,