2E18!"#$%&'()*+,-./01234(5+,6789:7;<=>?@;(.ABCD) E FG; H

IJK; L&MN'OPQ!"#$R,STUV7W&TX7/YZ9[7\]7^_'T`a>'b/c
defgTh+,7b/cdefR,iC=O j7klmno4Tpqpqrs>'0123t*u4
gvwxQP*yuxST!"#$%&4zqx* [1]yu701237R{'S8|}*gT./0
123g~{}*4PgUVmQP*yu7./0123ST

%&'*!"#$R,gefP/Y>9't*7}TX7/Y>9S!"#$R,7/Y,'Q* [2]yT!"#$R,7"47('fPQ p^7¡T(1)!"#$%&¢£'*+,¤¥¦7§¨T(2) !"#$SmV©ª«#$d+,¬­'f+,¦7®¯T'fPQ?@d°_^%±d²tyI!"#$%&'(t*!"#$R,7"K; !"#$R,Sj³´µ'OPQT¶·¸¹¥º7º,»gL = 1 }T¼f7½´µ (ML = 1, 0,–1) dfgTuxw¾¿'OPQT/Y,SÀÁ4m* [3]yÂqTML = 0 ´µSpx2py2pz /,ÃÄd4*gTzÅ7/,Æ[ghÇÅÈ]P^_'T/Y,7zz£+i!zz4ÉVoSÊ4m*yu7/Y,SË+'BVTÂqÌÍlR,S!zz = 2.954 ea02}TzÎ 3ÅÏx^Ð7/WS 9.009 Ñ10-3 Ehe-1a0-1i= 4.633 Ñ109 V m-1TÒÓÏ'OÔ*/W7B]4pQS
0.2896 e7/c't*74ÒÕo 'm*IMP2/LanL2DZÖ×ª7ØÙK [4]yuxSTh+,47./0123'Ë+mB]}*y; ÚÛp^!"#$R,7W&'ST¼f7½´µd?V'SÜWdÝÔ*Þg}*gTL&M
N7!"#$R,7W&'ST%&ÅizÎ4t*o7pz ¶·gß%&9¶·'àt*^_Tá
'px2py2pz /,ÃÄd4*yâã'OPQST %&¢£'*+,ä7/c7å7^_'Tb/
cdfgTXx'æçQ/Y,7è±g0é>'BPêëìgTpqpqíwx*yp^gQT!"#$%&7¢£îST!"#$R,'ï¿ð)QP*9:}*4ñ*yI!"#$%&¢£'*+,¤¥¦7§¨K; òfÉ7ó$ô:õö÷ø01236'OPQTö÷ø+,¬­7!"#$R,4ó$ô:~ù7úûüj C=O 7-7!"#$%&¢£gTX ý?@'þÿ]xQP* [5]yXuT~ùúûüj7!ü"#ëü7"gTu7!"#$%&¢£'Qn7'§¨]x*

Éd$%p^y; #&ª64pQN-methylacetamide-d1 (NMA-d1, CH3CONDCH3) 4 1-bromo-2,3,5,6-tetrafluorobenzene701236dé''TB3LYP/6-31+G(2df,p) Ö×ª7ØÙd(^4u)TÚÛNMA-d1'æçQT!ü"#ëü7¤¥»g* –11 cm-1+,-p (1715.3 " 1704.4 cm-1)T./[g* 200 km mol-101p^ (314.7 " 514.7 km mol-1)yuxdTNMA-d14D2O¼+,7012367W& (freq shift = –59.2 cm-1,IR int change = +213.2 km mol-1) 4æç*4T¤¥»+,-S 1/5 2[}*gT./[0BSÒ2[}*u4g)É*yC=O%&73>m./0123Ð4pQ4)x*r = 0.7 rO + 0.3 rC 'OÔ*T+,-0123/W7B]ST5ã7W& 3.97 # 10-3 Ehe-1a0-1 }TBrR,7/Y,7àgBPg [4]Tâã (20.40 # 10-3 Ehe-1a0-1) 4æç*4 1/5 2[}2

Tux'¤¥»+,-70;S|<*y./[0BgÒ2[4m*=©>?@'fPQST]w'$%dt*gT!"#$%&
67m9:}*Aî9g}*y31; ÒB7%±STCD6dEp^ 4,5,6,7-tetrabromobenzotriazole (TBB)
4glycine tripeptide-d3 [CH3CO-(Gly-d)2-NDCH3] 701236i67od
é'4p^ØÙFwx^yTripeptideN7¾úûüj7¤¥daverage partial vectorG [6] 'HIpQ?@p^4u)TC–Br4JK0123t*úûüj7L¼7 !ü"¤¥'T²4ÒB7¤¥»+,-4./[ML (peptide 1: –7.2 cm-1, +188.2 km mol-1; peptide 3:–13.9 cm-1, +220.8 km mol-1) gíwx^y

6 7 8 TBB 4 glycine tripeptide-d3 7012367
9:I©ª«#$d+,¬­'f+,K0

ST+,¬­R,ä7/,ÃÄ79't*^_TR-2<>'S!"#$'R^7SmPyÈ+,7Â4pQ-4±Sx'VPyuuSTÄXjè±'*YZg*Aî97}*Â4pQTû[×$\,]^$ (Ph2C=S) mnd
é'4p^?@d(^yØÙÖ×ªSMP2/6-31G*4p^y; _ÄX7Ph2C=O, Ph2C=S, Ph2C=SeST`,#ë=$-gaQ $z = –2.9 D2[}IbpzÎSC"Z (Z = O, S, Se) Å4t*K
TC=Z%&OP7/WS–zÅ}*ypÉpT
×$c$ddperfluoroÄXp^ (C6F5)2C=ZST$z gbef
}*77TZ = S, Se7W&'S_QÈ]Pi$z = –0.236,–0.002 DoyC=Z%&OPizÎoOgXx'hJmUÅixÎo7TXxixEz4Exi/ÅdÊef4t*od"j-p^7dT6Ç' tyZ = S, Se7W&'STR,kl-1-3%&7Bm97^_'T¬­R,7/Y,7è

Electric Field / 10 Ehe a0

STCS2gSTwx* [2] gTUV>'STC=SWPSC=Se-1; 5¿N'²p^'T%&OP7/Å7/W7Q£(a)-6210-1(b)-24(c)20-234567
Distance from O, S, or Se / Å

6Ç8(a) (C6F5)2C=O, (b) (C6F5)2C=S, (c)(C6F5)2C=Se7C=Z%&OPizÎo7
4ÒB7R,ä/,+m79't*Êef7!zz| E i.ýo4TXx'hJmUÅixz<*y+,no7./p$+qª¦7,$rÉ Îo7Exi{ýoIMP2/6-31G*Ö×ws_^tST!zz(S) = 1.163 ea02, !zz(Se) = 1.576 ea02}T ª7ØÙtKy'OPQzÎ7EzSÊTxÎ7ExSb}T!"#$R,CS2OgCSe27t!zz(S) = 1.166 ea02, !zz(Se) = 1.544 ea024
uvpQP*yp^gQTuxwSC=SOgC=Se%&797§¨gwx'xmP´y'OÔ*TSOgSeR,7æz>UV>m9:4wx*y%[1] P. Metrangolo et al., Acc. Chem. Res. 38, 386 (2005). [2] H. Torii, J. Chem. Phys. 119, 2192 (2003). [3] L. D. Landau andE. M. Lifshitz, Quantum Mechanics (Non-Relativistic Theory) Third Edition, Pergamon Press (1977). [4] H. Torii and M.
Yoshida, J. Comput. Chem., in press. [5] A. R. Voth and P. S. Ho, Curr. Topics Med. Chem. 7, 1336 (2007). [6] H. Torii, J.
Phys. Chem. A 108, 7272 (2004).