Calculating Accurate Proton Chemical hifts of rganic Molecules with Density Functional Methods and Modest Basis ets Rupal Jain,, # Thomas Bally,, * and Paul Rablen $, * Department of Chemistry, University of Fribourg, C-17 Fribourg, witzerland and Department of Chemistry, warthmore College, warthmore, PA 1981-1397 upporting Information 1. Complete Reference 3 (Gaussian program)...2 2. The 8 Molecules in the test set (cf. Reference 13)...3 3. Results of calculations of 1 MR chemical shifts, molecules of the "probe set"...5 4. Regression plots for GIA WP4/cc-pVDZ CRF, ACD, and ChemDraw...6 5. istograms showing error distributions for different methods...7 ote: - A complete Gaussian input to run a set of calculations on the entire test set is provided separately as a text file - Excel spreadsheets with the raw data and their statistical workup, both for the test set and the probe set, are also provided as a separate part of the upporting Information The above files are contained in the zip archive "MR_Data.zip". University of Fribourg. E-mail: Thomas.Bally@unifr.ch # Current address: IIT Bombay, India $ warthmore College, E-mail prablen1.swarthmore.edu 1
1. Complete form of Reference 29 (Gaussian program): M. J. Frisch, G. W. Trucks,. B. chlegel, G. E. cuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K.. Kudin, J. C. Burant, J. M. Millam,.. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. calmani,. Rega, G. A. Petersson,. akatsuji, M. ada, M. Ehara, K. Toyota, R. Fukuda, J. asegawa, M. Ishida, T. akajima, Y. onda,. Kitao,. akai, M. Klene, X. Li, J. E. Knox,. P. ratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. tratmann,. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. chterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. alvador, J. J. Dannenberg, V. G. Zakrzewski,. Dapprich, A. D. Daniels, M. C. train,. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. rtiz, Q. Cui, A. G. Baboul,. ifford, J. Cioslowski, B. B. tefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al- Laham, C. Y. Peng, A. anayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Rev E.1, Gaussian, Inc., Wallingford CT, 24. 2
2. The 8 Molecules in the test set (cf. Reference 12), in the order in which they appear in the Excel spreadsheets that contain the full set of results (supplied as part of the upporting Information, cf. p. 1). C 3 3 C 3 C 3 C 3 C 3 C 2 C 3 C 3 C C 3 3 C C 3 C C C 3 C 3 C 2 3 C i 3 C C 3 3 C 3 C C 3 3 C C 3 C C 3 C C 3 C 3 3 C C 3 C 3 3 C 3 C C 3 3 C C 3 3C C 3 3 C 2 3 C 3 C C 3 C 3 C C 3 3 C C 3 (continued on next page) 3
The 8 Molecules in the test set (cf. Reference 12), continued 3 C C 3 3 C C 3 3 C C 3 3 C C 3 C 3 C C 3 3 C 3 3 C C 3 C C 3 3 C C 3 3 C 3 C C 3 F 2 C 3 C 3 C 3 C 3 A complete Gaussian input to run a set of calculations on the entire test set is provided as a separate part of the upporting Information. 4
3. Results of calculations of 1 MR chemical shifts, molecules of the "probe set" method a functional b basis set c CRFd rms error (unscaled) rms error (scaled) e rms error (test set) GIA WP4 cc-pvtz yes.18.134.112 GIA WP4 aug-cc-pvdz yes.186.113.13 GIA WP4 cc-pvdz yes.213.113.115 GIA WP4 6-31++G(d,p) yes.154.119.121 GIA WP4 6-31G(d,p) yes.176.1.119 GIA WP4 6-31G* yes.164.79.12 GIA WP4 cc-pvtz no.228.128.124 GIA WP4 aug-cc-pvdz no.175.112.112 GIA WP4 cc-pvdz no.296.118.146 GIA WP4 6-31++G(d,p) no.194.13.129 GIA WP4 6-31G(d,p) no.234.93.14 GIA WP4 6-31G* no.3.93.159 GIA B3LYP cc-pvtz yes.22.138.118 GIA B3LYP aug-cc-pvdz yes.239.122.16 GIA B3LYP cc-pvdz yes.226.118.132 GIA B3LYP 6-31++G(d,p) yes.19.122.132 GIA B3LYP 6-31G(d,p) yes.199.98.162 GIA B3LYP cc-pvtz no.224.169.143 GIA B3LYP aug-cc-pvdz no.26.133.133 GIA B3LYP cc-pvdz no.292.135.173 GIA B3LYP 6-31++G(d,p) no.189.116.153 GIA B3LYP 6-31G(d,p) no.236.17.188 a Method for calculating chemical shieldings (see "Methods" section); b B3LYP and WP4 are hybrid functional, c The basis sets are denoted by their corresponding keywords in Gaussian; pvdz and 6-31G denote doble zeta, pvtz a triple-zeta basis sets; d "yes" means that chloroform was included as a solvent in a PCM-CRF calculation, "no" refers to gas-phase calculations; e scaled chemical shift δ = (intercept - isotropic magnetic shielding) / slope; 5
6
45 4 35 3 GIA/B3LYP/aug-cc-pvDZ in C 3 in the gas phase rms error:.16 /.133 ppm 25 2 15 1 5 4 35 3 25 2 15 1 5 4 35 3 25 2 15 1 5 -.4 -.3 -.2 -.1. B3LYP/aug-cc-pvDZ GIA CGT rms error:.133 /.139 ppm -.4 -.3 -.2 -.1. WP4_aug-ccpVDZ_scrf WP4_aug-ccpVTZ_scrf rms error:.13 /.113 ppm +.1 +.2 +.3 pp m +.1 +.2 +.3 ppm -.4 -.3 -.2 -.1. 7 +.1 +.2 +.3 ppm