A sting in the tail of flexible molecules: spectroscopic and energetic challenges in the case of p-aminophenethylamine

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A sting in the tail of flexible molecules: spectroscopic and energetic challenges in the case of p-aminophenethylamine Isabella A Lobo, 1 David D. J. Wilson, 1 Evan Bieske, 2 and Evan G Robertson 1 * 1 Department of Chemistry and La Trobe Institute for Molecular Sciences (LIMS), La Trobe University, Bundoora, Victoria, 3086, Australia. 2 School of Chemistry, University of Melbourne, Victoria 3010, Australia. * Corresponding Author Phone: +61 3 94792583 Email: e.robertson@latrobe.edu.au Table of Contents Table S1: Calculated energies of PEA... 2 Table S2: Conformer preference of APEA with aromatic amine in up and down form... 3 Table S3: Calculated barriers between conformers of APEA... 4 Figure S1: Comparison of experimental IR spectra of APEA with computed stick spectra... 5 Notes on the vibrational scaling factors... 7 1

Supplementary Data Tables Table S1. Ab initio calculated relative energies of PEA conformers in kj mol -1. Conformer Aa Ag Ga Gg Gg' alternative label a (V) (IV) (II) (III) (I) Electronic B3LYP/aug-cc-pVTZ -0.08 0.56 0.43 0.00 5.81 MP2/6-311+G** 5.32 5.23 0.98 0.00 8.32 MP2/TZVP 6.10 6.39 0.36 0.00 8.12 MP2/TZVPP 5.11 6.74 1.26 0.00 8.21 CCSD-F12b/cc-pVDZ-F12 b 2.55 2.50 1.25 0.00 6.91 CCSD-F12b/cc-pVTZ-F12 b 2.63 2.54 1.28 0.00 7.01 CCSD-F12b/CBS b,c 2.66 2.56 1.29 0.00 7.05 CCSD(T)-F12b/cc-pVDZ-F12 b 3.05 3.30 1.14 0.00 7.22 CCSD(T)-F12b/cc-pVTZ-F12 b 3.23 3.45 1.16 0.00 7.40 CCSD(T)-F12b/CBS b,c 3.30 3.51 1.17 0.00 7.47 Zero point correction B3LYP/aug-cc-pVTZ -0.55-0.53-0.18 0.00-0.76 MP2/6-311+G** -1.00-1.00 0.24 0.00-1.18 MP2/TZVP -1.46-1.30-0.21 0.00-0.63 MP2/TZVPP -0.67-0.66-0.23 0.00-0.78 Gibbs free energy correction B3LYP/aug-cc-pVTZ -1.13-1.22-0.28 0.00-1.99 MP2/6-311+G** -3.38-3.24 0.35 0.00-2.89 MP2/TZVP -5.69-3.79-0.13 0.00-2.17 MP2/TZVPP -2.04-2.19-0.50 0.00-2.09 Gibbs Free Energy 298K CCSD(T)-F12b/cc-pVDZF12 d 1.92 2.08 0.87 0.00 5.23 CCSD(T)-F12b/cc-pVTZF12 d 2.10 2.23 0.89 0.00 5.41 CCSD(T)-F12b/CBS d 2.18 2.29 0.89 0.00 5.48 CCSD(T)-F12b/cc-pVDZF12 e 1.01 1.11 0.64 0.00 5.13 CCSD(T)-F12b/cc-pVTZF12 e 1.19 1.26 0.66 0.00 5.31 CCSD(T)-F12b/CBS e 1.26 1.33 0.67 0.00 5.38 a b c d e Alternative nomenclature CF1, CF2 for conformers of APEA, 6 and in parentheses the labels I-V for 4, 9-11 corresponding conformers of PEA. Single-point energy at MP2/6-311+G** optimized geometries. CBS extrapolation from cc-pvdz-f12 and cc-pvtz-f12 relative energies. B3LYP/aug-cc-pVTZ Gibbs correction. MP2/aug -cc-pvtz Gibbs correction. 2

Table S2. Ab initio calculated energy differences (in kj mol -1 ) between APEA with the aromatic amine in up and down configurations. A positive value indicates that the down configuration is lower in energy. Conformer Aa Ag Ga Gg Gg' alternative label a CF1 CF2 CF3 CF4 CF5 (V) (IV) (II) (III) (I) Electronic energy (E e ) B3LYP/6-31+G* -0.08 0.14 0.13 0.36-0.02 B3LYP/6-31++G** -0.04 0.17 0.14 0.36 0.01 B3LYP/6-311+G** -0.05 0.14 0.12 0.31 0.00 MP2/TZVPP -0.08 0.14 0.04 0.33-0.12 CCSD-F12b/cc-pVDZ-F12 b 0.22 0.39 0.43 0.68-0.14 CCSD(T)-F12b/cc-pVDZ-F12 b 0.18 0.35 0.37 0.63-0.15 E 0 (including Zero-point correction) B3LYP/6-31+G* -0.08 0.10 0.04 0.27 0.00 B3LYP/6-31++G** -0.06 0.10 0.03 0.23 0.01 B3LYP/6-311+G** -0.04 0.11 0.04 0.23 0.04 MP2/TZVPP -0.04 0.14 0.08 0.31-0.16 G 298K (Gibbs free energy) B3LYP/6-31+G* -0.11 0.07 0.01 0.14 0.22 B3LYP/6-31++G** -0.08 0.06 0.00 0.10 0.05 B3LYP/6-311+G** -0.09 0.04-0.03 0.05 0.04 MP2/TZVPP -0.05 0.12 0.09 0.28-0.31 CCSD(T)-F12b/cc-pVDZ-F12 b,c 0.16 0.30 0.27 0.44-0.04 CCSD(T)-F12b/cc-pVDZ-F12 b,d 0.21 0.33 0.42 0.57-0.34 a b c d Alternative nomenclature CF1, CF2 for conformers of APEA, 6 and in parentheses the labels I-V for 4, 9-11 corresponding conformers of PEA. Single-point energy at MP2/6-311+G** optimized geometries. B3LYP/6-311+G** zero-point energy and Gibbs energy correction. MP2/TZVPP zero-point energy and Gibbs energy correction. 3

Table S3. MP2/6-311+G** calculated barrier heights (in kj mol -1 ) for rotational between conformers. Data is presented as Gibbs free energy ( G) differences between minima and transition state and refers to the energy difference from the conformer labelled on the left. Values in parentheses are B3LYP/6-311+G** results. Conformer Aa Ag Ga Gg Gg' alternative label a CF1 (V) CF2 (IV) CF3 (II) CF4 (III) CF5 (I) Aa (CF1) - 10.4 (9.4) 20.0 (18.4) 20.0 (18.4) 19.6 (17.5) Ag (CF2) 10.2 (8.6) - 13.1 (13.0) 19.4 (17.1) 16.7 (16.9) Ga (CF3) 21.3 (17.7) 14.7 (13.1) - 10.7 (10.9) 13.4 (13.1) Gg (CF4) 22.9 (17.4) 22.6 (17.5) 12.3 (11.2) - 8.0 (8.5) Gg (CF5) 14.3 11.3) 11.5 (11.4) 6.8 (7.5) 2.7 (2.7) - a Alternative nomenclature CF1, CF2 for conformers of APEA, 6 and in parentheses the labels I-V for 4, 9-11 corresponding conformers of PEA. 4

Supplementary Data Figures Figure S1. Comparison of experimental IR spectra of APEA with computed stick spectra in which IR intensities in km mol -1 are divided by 100. Top trace: harmonic M06-X2/aug-cc-pVTZ (scaled 0.946). 2 nd trace: unscaled anharmonic B3LYP/6-311+G**. 3 rd trace: harmonic B3LYP/aug-ccpVTZ (scaled 0.96). 5

6

Notes on the vibrational scaling factors used in spectral simulations A preliminary investigation of suitable scaling factors for MP2 and B3LYP with a 6-311+G** basis, using spectroscopic data from aniline, ethylbenzene, methylamine and ethylamine determined the following set of empirical scaling factors for the different types of stretch modes: Method aliphatic-ch aromatic-ch aliphatic-nh aromaticc-nh MP2 0.9387 0.9484 0.9425 0.9536 B3LYP 0.9614 0.9602 0.9568 0.9580 1. MP2/TZVPP (scaled 0.94) As stated in the table 2 footnote, MP2/TZVPP wavenumber values were scaled by 0.94. This value was selected to allow the best prediction of aliphatic CH stretch modes, and is also identical to the value chosen for CH and OH stretch modes computed at the MP2/aug-cc-pVTZ level in the study of Myshakin et al.[ref 64]. We note however that this does not match the optimal scaling factor for the anilinic NH stretch modes from the list above, and the predictions for the corresponding vibrations in figure 5 are correspondingly too low. 2. B3LYP/aug-cc-pVTZ (scaled 0.96). Unlike the MP2 case, for B3LYP a single scaling factor of 0.96 is broadly suited to all the CH and NH stretch modes. Note that in the study of Halls et. al., a similar scaling factor of 0.9659 is recommended for modes over 1800 cm-1 computed at the B3LYP/pVTZ level, and is reported to produce a standard deviation of 39 cm -1. [Halls, M. D.; Velkovski, J.; Schlegel, H. B., "Harmonic Frequency Scaling Factors for Hartree- Fock, S-VWN, B-LYP, B3-LYP, B3-PW91 and MP2 with the Sadlej pvtz Electric Property Basis Set," Theor. Chem. Acc., 2001, 105, 413-421] 3. M06-2X/aug-cc-pVTZ (scaled 0.946) The scaling factor of 0.946 is consistent with those reported in Alecu et. al. for fundamental wavenumber values: M06-2X/aug-cc-pVTZ 0.946 standard deviation 48 cm -1 M06-2X/def2-TZVPP 0.945 standard deviation 48 cm -1 [I. M. Alecu, Jingjing Zheng, Yan Zhao, and Donald G. Truhlar, J. Chem. Theory Comput. 2010, 6, 2872 2887] 7

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