FIGURES for Altun-Trindle

SUPPLEMENTARY TABLES for Altun-Trindle

Table S1: performance of model chemistries in various basis sets for Stephens’ reference set of small and medium-sized organic molecules (B3LYP).

Model / MAD
HF/6-31G(d) / 35.3
HF/aug-cc-pVDZ / 35.5
B3LYP/6-31G(d) / 25.6
B3LYP/6-311++G(2d,2p) / 18.7
B3LYP/aug-cc-pVDZ / 20.1
B3LYP/aug-cc-pVTZ / 23

MAD is the mean absolute deviation of the computed absolute optical rotation from experimental values of absolute rotation at the sodium D line at 589 nm (degrees). In arriving at these statistics the authors omitted two serious outliers.

Table S2: mean absolute deviation (MAD) in Stephens’ test set according to various pure density functional models.

Model / MAD
LDA/IV / 51
GGA/IV / 43
LDA/Vp / 23
GGA/Vp / 19
LDA/Vd / 25
GGA/Vd / 24
SAOP/Vd / 20

The choice for the Local Density Approximation (LDA) is the Vosko-Wilk-Nusair (VWN) functional ; for the Generalized Gradient Approximation (GGA), the Becke-Perdew 86 functional. IV is a DZ quality basis with polarization by one set of d functions on heavy atoms CNO and one set of p functions on each H atom. Vp is an TZ quality basis extensively polarized with two sets of d and two sets of f functions on heavy atoms CNO and three sets of p and two sets of d functions on each H atom. Vd is a TZ basis with d and f polarization sets on CNO and p and d sets on H atoms, augmented by diffuse s, p, and d sets on CNO and two diffuse p sets on H atom. MAD is the mean absolute deviation from experimental values of absolute rotation angles (degrees).

Table S3: Experimental estimates and computed values for excitation energies E in eV and rotational strengths R in 10-40 cgs units for dimethyloxirane.

State / Exp(a) / Exp(b) / HF (c) / MR-CI (d) / DFT RPA (e)
1B
ΔE (eV) / 6.98 / 7.06 / 6.36 / 6.98* / 7.04
R / -10.1 / -20.0 / -3.04 / -7.63 / -10.9
1A
ΔE / 7.39 / 7.45 / 6.64 / 7.31 / 7.41
R / 0.2 / 0.4 / 4.1 / 10.8 / 12.6
2A
ΔE / 7.59 / 7.74 / 7.18 / 7.46 / 7.47
R / -6.2 / -14 / -0.42 / -5.65 / -4.9
2B
ΔE / 8.16 / 7.08 / 7.70 / 7.66
R / 2.3 / -0.74 / -1.44 / -5.5

*Excitation energies shifted so to match the lowest energy transition observed in Exp(a).

(a)Breest et. al l2 (b) Cohen et al.13(c) Carnell, et al.14 (d) Grimme and Peyerimhoff

Table 4: Time-dependent (linear response) density functional estimates of the CD spectrum of dimethyl oxirane

SAOP
TZP / SAOP
ATZP / SAOP
Vdiff (a) / ADF
TZP / ADF
TZ2P / ADF
ATZP / ADF
ATZ2P / G03*
medium / G03*
Pref
1B
ΔE / 6.95 / 6.91 / 6.92 / 6.07 / 6.10 / 5.03 / 5.36 / 6.79 / 6.50
R / -12 / -17 / -15.0 / -13 / -13 / -29 / -17 / -17 / -14
2A
ΔE / 7.23 / 7.39 / 7.26 / 6.43 / 6.45 / 5.35 / 5.65 / 7.18 / 6.88
R / 3 / 4 / 2.28 / 9 / 9 / 13 / 10 / 18 / 13
3A
ΔE / 7.43 / 7.45 / 7.42 / 6.57 / 6.58 / 5.46 / 5.76 / 7.24 / 6.94
R / 15 / -10 / -4.64 / 13 / 12 / -4 / -1 / -9 / -3
2B
ΔE / 7.88 / [7.87] / 7.76 / 7.33 / 7.35 / 5.74 / 6.08 / 7.51 / 7.11
R / 25 / [-10] / -17.6 / -13 / -14 / -18 / -16 / -15 / -14

TD-DFT-based characterization of the 2,3-dimethyloxirane spectrum. Basis sets: TZP=triple-zeta split-valence set and polarization on heavy atoms; TZ2P adds polarization on H atoms; Axyz invokes diffuse functions in addition to the multiple-zeta and polarization already defined. Vdiff has polarization and diffuse functions and is defined in source (a). SAOP redefines the functional by “statistical averaging of orbital potentials”, as in (b). This work uses a PBE density functional for exchange and correlation for structures and non-SAOP TD-DFT results. Excitation energies are reported in electron volts, rotational strength parameters are in cgs units ( 1040)

Table S5: SAOP and B3LYP models of the CD spectrum for Oxaadamantanedione

SAOP-ATZP / B3LYP/preferred
E(eV) / Mean R / E(eV) / Mean R
3.7271 / 18.7 / 3.9490 / 4.1
3.7752 / -0 / 4.0159 / 0.2
4.2142 / -23.9 / 4.9371 / 0
5.4521 / 4.0 / 4.9523 / -0.5
5.5071 / 9.7 / 5.5825 / -0.8
5.6651 / 2.2 / 6.0296 / 15.2
6.0602 / -1 / 6.0818 / -0.5
6.0785 / 3.7 / 6.1404 / 9.1
6.6339 / -21 / 6.2487 / 8.1