Supporting Information

Transcription

1 Supporting Information Zhang et al /pnas Fig. S1. The enlarged figure for Bz-CH 4, which shows that the agreement between XYG3 and CCST(T) is quite good but not perfect. Some errors remain. 1of6

2 Table S1. Heats of formation (kcal/mol) at 298 K for the G3/99 set with 223 species No. Molecule name Total expt. Error B3LYP Error M06-2x Error XYG3 MAD Max (SF 6 ) (O 3 ) (SF 6 ) Max (BeH) (P 4 ) 6.28 (BCl 3 ) 1 H LiH BeH CH CH 2 ( 3 B 1 ) CH 2 ( 1 A 1 ) CH CH NH NH NH HO HOH HF SiH 2 ( 1 A 1 ) SiH 2 ( 3 B 1 ) SiH SiH PH PH H 2 S HCl Li LiF C 2 H H 2 CACH C 2 H CN HCN CO HCO H 2 CAO CH 3 OH N H 2 NONH NO O HOOH F CO Na Si P S Cl NaCl SiO CS SO ClO ClF H 3 SiOSiH CH 3 Cl H 3 COSH HOCl SO BF BCl AlF AlCl CF of6

3 No. Molecule name Total expt. Error B3LYP Error M06-2x Error XYG3 62 CCl OACAS CS COF SiF SiCl N 2 O ClNO NF PF O F 2 O ClF C 2 F C 2 Cl CF 3 CN Propyne Allene Cyclopropene Propylene Cyclopropane Propane Butadiene butyne Methylene cyclopropane Bicyclobutane Cyclobutene Cyclobutane Isobutene Trans butane Isobutene Spiropentane Benzene H 2 CF HCF H 2 CCl HCCl Methylamine Methyl cyanide Nitromethane Methyl nitrite Methyl silane Formic acid Methyl formate Acetamide Aziridine Cyanogens Dimethylamine Trans ethylamine Ketene Oxirane Acetaldehyde Glyoxal Ethanol Dimethylether Thiooxirane Dimethyl sulfoxide Ethanethiol Dimethyl sulphide H 2 CACHF ethyl chloride Vinyl chloride Acrylonitrile Acetone Acetic acid of6

4 No. Molecule name Total expt. Error B3LYP Error M06-2x Error XYG3 127 Acetyl fluoride Acetyl chloride Propyl chloride Isopropanol Methyl ethyl ether Trimethylamine Furan Thiophene Pyrrole Pyridine SH CCH C 2 H 3 ( 2 A ) CH 3 CO ( 2 A ) H 2 COH ( 2 A) CH 3 O( 2 A ) CH 3 CH 2 O( 2 A ) CH 3 S( 2 A ) C 2 H 5 ( 2 A ) (CH 3 ) 2 CH ( 2 A ) (CH 3 ) 3 C NO Methyl allene Isoprene Cyclopentane n-pentane Neopentane ,3-cyclohexadiene ,4-cyclohexadiene Cyclohexane n-hexane methyl pentane Toluene n-heptane Cyclooctatetraene n-octane Naphthalene Azulene Methyl acetate t-butanol Aniline Phenol Divinyl ether Tetrahydrofuran Cyclopentanone Benzoquinone pyrimidine Dimethyl sulphone Chlorobenzene ,2,-dicyano ethane Pyrazine Acetyl acetylene Crotonaldehyde Acetic anhydride ,5-dihydrothiophene Isobutane nitrile Methyl ethyl ketone Isobutanal ,4-dioxane Tetrahydrothiophene t-butyl chloride n-butyl chloride Tetrahydropyrrole Nitro-s-butane Diethyl ether of6

5 No. Molecule name Total expt. Error B3LYP Error M06-2x Error XYG ,1-dimethoxy ethane t-butanethiol Diethyl disulfide t-butylamine Tetramethylsilane methyl thiophene n-methyl pyrrole Tetrahydropyran Diethyl ketone Isopropyl acetate Tetrahydrothiopyran Piperidine t-butyl methyl ether ,3-difluorobenzene ,4-difluorobenzene Fluorobenzene Di-isopropyl ether PF SF P SO SCl POCl PCl Cl 2 O 2 S PCl Cl 2 S SiCl CF 3 Cl C 2 F CF Phenyl radical Expt. is the total experimental value from ref. 12. For each method the errors is quoted as [experiment theory] from single-point calculations with the G(3df,2p) basis set at the geometry optimized with B3LYP using the G(d,p) basis set. MADs, with the largest positive error (Max( ) energy too high) and the largest negative error (Max( ) energy too low). 5of6

6 Table S2. Numerical accuracy by using Eq. 5 with SVWN/6-311 G(3df,2p) for several atoms Atoms Ex(HF) Ex(S) Ec(VWN) Exc-HH Eq. 5 Exc-HH Becke H He Li Be B C N O F Ne Becke approximated U xc, 1 U LDA xc with LDA given by PW91 [Perdew JP Wang Y (1992) Accurate and simple analytic representation of the electron-gas correlation energy. Phys Rev B 45:13244]. In this prescription, the XC potential must be in the energy expression. Instead, it is common to approximate the Becke half-and-half as in Eq. 5 for easy implementation. Using the common LSD and/or GGA correlation functionals, which are averaged, as a replacement for the upper limit of the integral over is not strictly consistent with the AC formula. Nevertheless, the numbers in column 5 are close to those in column 6. It should be noted that Becke calculations were performed fully numerically and basis-set free in a post-lda manner [Becke AD (1993) A new mixing of Hartree Fock and local density-functional theories. J Chem Phys 98:1372]. All energies are in au. 6of6