1 Supporting information Time-Resolved Spectroscopic Characterization of a Novel Photodecarboxylation Reaction Mediated by Homolysis of a Carbon α Bond in Flurbiprofen Authors: Tao Su, Jiani Ma, Naikei Wong and David Lee Phillips* Department of Chemistry, the University of Hong Kong, Pokfulam Road, Hong Kong P.R. China Journal: The Journal of Physical Chemistry B Ms. No. jp-2013-03053f Table of Contents Figure 1S. The predicted absorption spectrum of the ground state Fp obtained from TD-DFT calculations done at the B3LYP/6-31G (d,p) level of theory is presented. ........................................ S3 Figure 2S. Shown are the DFT calculated frontier orbitals of ground state Fp involved in the HOMO-2, HOMO-1, HOMO, LUMO ............................................................................................... S4 Figure 3S. Shown are the optimized geometries of the RC1, TS 1 , and PC 1 /RC 2 obtained from the UB3LYP/6-31G (d,p) calculations for the hydrogen transfer process through two steps. ................. S4 Figure 4S. Shown are the optimized geometries of the RC, TS, and PC obtained from the UB3LYP/6-31G (d,p) calculations for the hydrogen transfer process through one step. ................... S5 Complete author lists for references 33 and 55……………………………………………………...S5 Table 1S. Excited-State Energies and Oscillator Strengths determined from TD-DFT B3LYP/6-31G (d,p) Calculations for the ground state Fp are listed. .......................................................................... S6 Table 2S. Comparison of the experimental resonance Raman spectrum vibrational frequencies in MeCN with the DFT calculated vibrational frequencies for the ground state Fp with preliminary vibrational assignments and qualitative descriptions of the vibrational modes in the 800-1800 cm -1 region are shown. ................................................................................................................................ S7 Table 3S. Excited-State Energies and Oscillator Strengths determined from TD-DFT B3LYP/6-31G (d,p) Calculations for the T 1 are listed. ............................................................................................... S8 Table 4S. Excited-State Energies and Oscillator Strengths determined from TD-DFT B3LYP/6-31G (d,p) Calculations for the FpR are listed ............................................................................................. S9 Table 5S. Excited-State Energies and Oscillator Strengths determined from TD-DFT B3LYP/6-31G (d,p) Calculations for the FOR are listed .......................................................................................... S10 Table 6S. A comparison of the experimental 0 ns TR 3 spectrum vibrational frequencies obtained in MeCN with the DFT calculated vibrational frequencies for the T 1 and FpR intermediates along with preliminary vibrational assignments and qualitative descriptions of the vibrational modes in the