Structural features of the carbon-sulfur chemical bond: a semi-experimental perspective Supporting Information Emanuele Penocchio, Marco Mendolicchio, Nicola Tasinato, and Vincenzo Barone∗ Scuola Normale Superiore, Pisa, Italy E-mail: [email protected] ∗To whom correspondence should be addressed 1 In Table 1 we focus on molecules reported in Table 2 of the main article and compare reference SE equilibrium parameters with ab-initio predictions obtained with B3LYP/SNSD, B2PLYP/VTZ, M06-2X, and BHandH model chemistries. β In Table 2, experimental rotational constants, ∆Bvib calculated at B3LYP/SNSD and B2PLYP/VTZ β levels of theory, and ∆Bel calculated at B3LYP/AVTZ level are reported for all the species discussed in the main text. Table 1: Comparison between reference SE equilibrium parameters and ab-initio ones ob- tained using functionals with a different amount of Hartree-Fock exchange (see main text). Distances in A,˚ angles in degrees. Atom numbering as in Figure 2 of the main work. SEa re re B3LYP/SNSD B2PLYP/VTZ M06-2X/VTZ BHandH/VTZ SE { Sulfur chains { isothiocyanic acid r(S-C) 1:5832 1:5744 1:5713 1:5588 1:5678(7) r(C-N) 1:2091 1:2047 1:1922 1:179 1:2047(9) r(N-H) 1:0102 1:0035 1:0035 0:9974 1:0070(9) a(S-C-N) 173:77 173:95 174:81 175:42 172:23(18) a(H-N-C) 129:67 131:50 134:72 137:28 129:75(5) thioformaldehyde r(S-C) 1:6227 1:6135 1:60089 1:58782 1:6093(1) r(C-H) 1:0918 1:0859 1:08702 1:0849 1:0854(2) a(H-C-S) 121:95 122:01 122:025 121:964 121:73(2) thioketene r(S-C) 1:5724 1:5623 1:5546 1:5426 1:5556(4) r(C-C) 1:3107 1:3082 1:3021 1:2899 1:3107(5) r(C-H) 1:0863 1:0801 1:0811 1:0793 1:0806(1) a(C-C-H) 120:66 120:46 120:31 129:34 120:15(1) propadienethione r(S1-C2) 1:5876 1:5776 1:5673 1:5546 1:5715(15) r(C2-C3) 1:2722 1:2691 1:2679 1:2571 1:2702(18) r(C3-C4) 1:3223 1:3191 1:3119 1:3003 1:3228(9) r(C4-H) 1:0905 1:0848 1:0851 1:0832 1:0842(3) a(H-C4-C3) 121:80 121:68 121:48 121:49 121:20(2) 2 β β Table 2: Experimental rotational constants, ∆Bvib, and ∆Bel are reported for all the species discussed in the main text. All data are in MHz, see main text for atom numbering. β EXP β β (B0 ) −∆Bvib ∆Bel B3LYP/SNSD B2PLYP/VTZ B3LYP/AVTZ thiirane parent A 21973:6349a 200:215 211:715 −0:196 B 10824:8925a 65:624 68:231 −0:153 C 8026:24744a 65:267 68:182 0:212 33S A 21973:4850b 200:338 211:838 −0:196 B 10683:8236b 64:437 67:002 −0:148 C 7948:33140b 64:331 67:208 0:208 34S A 21973:3890b 200:467 211:955 −0:196 B 10551:1131b 63:331 65:852 −0:143 C 7874:59486b 63:451 66:291 0:205 13C A 21482:4120b 192:968 204:216 −0:187 B 10653:3545b 63:839 66:401 −0:150 C 7866:25519b 63:373 66:234 0:202 4D A 15471:0c 125:390 130:939 −0:096 B 9197:6c 53:388 54:908 −0:116 C 6819:0c 50:661 52:345 0:150 thiazole parent A 8529:403d 65:070 66:728 −0:509 B 5505:746d 31:412 32:566 −0:261 C 3344:291d 23:458 24:190 0:074 34S A 8529:220d 64:950 66:612 −0:509 B 5353:320d 30:318 31:417 −0:247 C 3287:440d 22:898 23:610 0:071 15N A 8471:550d 64:081 65:736 −0:498 B 5401:340d 30:682 31:870 −0:253 C 3296:756d 22:959 23:701 0:072 13 d C2 A 8335:696 63:323 64:956 −0:485 B 5504:919d 31:037 32:201 −0:262 C 3313:801d 23:103 23:834 0:072 13 d C4 A 8460:999 64:179 65:865 −0:505 B 5412:722d 30:737 31:817 −0:251 C 3299:390d 23:007 23:714 0:072 13 d C5 A 8317:847 62:972 64:590 −0:484 B 5505:989d 31:185 32:327 −0:261 C 3311:352d 23:108 23:828 0:072 d D2 A 7867:590 57:225 58:656 −0:433 B 5505:486d 31:441 32:560 −0:261 C 3237:439d 22:304 22:982 0:069 d D4 A 8325:228 63:225 64:838 −0:499 B 5229:035d 29:128 30:122 −0:230 C 3210:280d 22:063 22:727 0:068 d D5 A 7855:939 56:097 57:527 −0:429 B 5498:517d 31:716 32:895 −0:263 C 3233:047d 22:211 22:910 0:069 References: a) 1; b) 2; c) 3; d) 4; 3 | Table 2 continued | β EXP β β (B0 ) −∆Bvib ∆Bel B3LYP/SNSD B2PLYP/VTZ B3LYP/AVTZ 1,2,3-thiadiazole parent A 8711:38a 65:265 67:814 −0:840 B 5847:09a 43:587 46:446 −0:319 C 3496:59a 28:651 30:087 0:072 34S A 8711:41a 65:140 67:628 −0:841 B 5686:12a 42:073 44:872 −0:301 C 3438:37a 28:016 29:431 0:070 15 a N2 A 8502:61 63:456 65:949 −0:797 B 5846:91a 43:211 45:961 −0:319 C 3462:38a 28:199 29:580 0:071 15 a N3 A 8650:57 63:832 66:238 −0:821 B 5740:43a 42:986 45:770 −0:310 C 3448:54a 28:150 29:538 0:070 13 a C4 A 8641:88 65:077 67:632 −0:836 B 5742:95a 42:139 44:936 −0:304 C 3448:07a 28:040 29:460 0:070 13 a C5 A 8486:04 62:670 65:041 −0:799 B 5847:30a 43:416 46:235 −0:319 C 3459:77a 28:139 29:522 0:070 a D4 A 8518:49 65:578 68:230 −0:826 B 5530:15a 39:050 41:553 −0:276 C 3351:31a 26:793 28:134 0:066 a D5 A 7998:72 55:213 57:234 −0:704 B 5839:27a 44:759 47:498 −0:321 C 3373:24a 27:162 28:422 0:067 34 a S, D5 A 7997:22 55:168 57:183 −0:705 B 5680:08a 43:149 45:841 −0:303 C 3319:24a 26:586 27:841 0:065 15 a N2,D5 A 7815:75 53:726 55:746 −0:668 B 5838:42a 44:426 47:025 −0:322 C 3339:97a 26:728 27:935 0:066 15 a N3,D5 A 7949:74 53:942 55:844 −0:687 B 5728:83a 44:165 46:728 −0:313 C 3327:53a 26:706 27:888 0:065 13 a C4,D5 A 7939:11 55:271 57:341 −0:703 B 5737:70a 43:209 45:904 −0:306 C 3328:66a 26:605 27:868 0:065 13 a C5,D5 A 7816:59 53:038 55:006 −0:673 B 5839:34a 44:644 47:317 −0:322 C 3340:43a 26:678 27:896 0:065 2D A 7831:12a 56:160 58:338 −0:698 B 5528:41a 39:932 42:295 −0:277 C 3238:85a 25:479 26:665 0:061 References: a) 5. 4 | Table 2 continued | β EXP β β (B0 ) −∆Bvib ∆Bel B3LYP/SNSD B2PLYP/VTZ B3LYP/AVTZ 1,3,4-thiadiazole parent A 8907:376a 72:606 74:365 −0:599 B 5569:321a 30:842 32:573 −0:336 C 3424:779a 24:590 25:555 0:061 34S A 8907:484a 72:442 74:265 −0:599 B 5408:526a 29:745 31:414 −0:317 C 3363:296a 23:962 24:916 0:058 15N A 8838:554a 71:489 73:271 −0:590 B 5469:994a 30:167 31:892 −0:323 C 3376:938a 24:078 25:044 0:059 13C A 8696:617a 70:552 72:217 −0:571 B 5569:263a 30:531 32:225 −0:335 C 3393:119a 24:248 25:179 0:060 2D A 7565:918a 55:432 56:874 −0:431 B 5567:338a 31:016 32:603 −0:335 C 3205:561a 22:161 22:991 0:053 34S, 2D A 7566:044a 55:306 56:759 −0:431 B 5407:324a 29:911 31:424 −0:318 C 3151:862a 21:641 22:451 0:051 15N, 2D A 7517:216a 54:713 56:151 −0:426 B 5467:128a 30:307 31:898 −0:323 C 3163:478a 21:724 22:555 0:052 13C, 2D A 7413:475a 53:955 55:397 −0:414 B 5567:237a 30:730 32:273 −0:335 C 3177:816a 21:835 22:647 0:052 D A 8190:071a 63:117 64:734 −0:506 B 5568:156a 30:962 32:572 −0:336 C 3312:800a 23:347 24:229 0:057 34S, D A 8189:876a 62:992 64:610 −0:506 B 5407:830a 29:860 31:407 −0:317 C 3255:322a 22:779 23:641 0:054 15N-D A 8134:555a 62:364 63:965 −0:499 B 5469:463a 30:244 31:825 −0:323 C 3268:673a 22:887 23:756 0:056 15N, D A 8130:079a 62:123 63:748 −0:499 B 5467:331a 30:293 31:883 −0:323 C 3267:174a 22:867 23:743 0:056 13C-D A 8019:104a 61:382 62:935 −0:485 B 5568:179a 30:648 32:244 −0:335 C 3284:460a 23:004 23:866 0:056 13C, D A 8004:030a 61:433 62:992 −0:483 B 5567:949a 30:642 32:245 −0:335 C 3281:849a 23:013 23:879 0:056 References: a) 6.