Supplementary Material for
“Solvent-mediated Internal Conversion in Diphenoxyethane-(H2O)n Clusters,
n=2-4”
Patrick S. Walsh, Evan G. Buchanan, Joseph R. Gord and Timothy S. Zwier
Department of Chemistry, Purdue University
560 Oval Drive, West Lafayette, IN 47901
Table of Contents
1. Summary of results from vertical excitation calculations using TDDFT (M05-2x/631+G(d)) including predicted UV excitation spectra, and the rendered molecular orbitals
involved in the π→π* transtions for the DPOE-(H2O)n (n=2-4) clusters (Figures S1-S4).
2. Complete list of the experimental ground and excited state vibrational frequencies for the
DPOE-(H2O)n (n=1-3) clusters (Table S1).
1. Results from TD-DFT Calculations on the DPOE-(H2O)n (n=2-4) Clusters
TD-DFT calculations were performed to predict the vertical excitation energies for the first
two singlet excited states. These results are summarized below as scaled stick spectra compared
to the experimentally recorded excitation spectra. Molecular orbitals for those involved in the
excitations were rendered and are plotted to show, nominally, which of the two π-systems were
undergoing the electronic excitation. Analysis of these results is consistent with the conclusions
that were gleaned through the analysis of the ES-RIDIR spectra.
Figure S1. The calculated UV spectrum for the [1:2] cluster (a), along with the structure of the [1:2] cluster (b). The calculated
weights and molecular orbitals for excitation to S1 and S2.
Figure S2. The calculated UV spectrum for the [1:3] cycle cluster (a), along with the structure of the [1:3] cycle cluster (b). The
calculated weights and molecular orbitals for excitation to S1 and S2.
Figure S3. The calculated UV spectrum for the [1:3] chain cluster (a), along with the structure of the [1:3] chain cluster (b). The
calculated weights and molecular orbitals for excitation to S1 and S2.
Figure S4. The calculated UV spectrum for the [1:4] cluster (a), along with the structure of the [1:4] cluster (b). The calculated
weights and molecular orbitals for excitation to S1 and S2.
2. Table of experimental vibrational frequencies for the DPOE-(H2O)n (n=1-3) clusters
in S0, S1, and S2
Table S1. Vibrational frequencies from the experimental RIDIR spectra in S0 , S1 , and S2 states for DPOE-(H2 O)n (n=1-3). S2 shows mixed
charater due to Kasha's and Fermi's Golden rule. The S1 transitions appearing in S2 are shown in parentheis.
-1
Structure/State
DPOE-H 2 O
a
DPOE-(H 2 O) 2
A-DPOE-(H 2 O) 3
a
Free
OH•••O, Ether
Vibrational Frequency (cm )
H2 O(1)→H2 O(2) H2 O(2)→H2 O(3) H2 O(3)→H2 O(1)
OH•••π
Water Label
OH(1)-Sym.
OH(1)-Asym.
S0
3597
3707/3705
S1
3598
3691
S2 (S1 )
3612 (3598)
3709 (3693)
Water Label
OH(2)
OH(1)-Sym.
OH(1)-Asym.
OH(2)
S0
3715
3550
3683
3486
S1
3714
3555
3645/3635
3485
S2 (S1 )
3713 (3714)
3579 (3555)
3684 (3650)
3493 (3489)
Water Label
OH(2)
OH(1)-Asym. OH(3)-Asym.
OH(1)-Sym.
OH(2)-Sym.
OH(3)-Sym.
S0
3706
3641
3653
3563
3384
3486
S1
3704
3646
3652
3560
3380
3486
S2 (S1 )
3704
3653
3661
3563
3382
3486
Values taken from E.G. Buchanan, J.R. Gord, and T.S. Zwier, J. Phys. Chem. Lett. 4, 1644 (2013).