-TFSI                   !  "     # $ %& ' () * + , - . ) / 0>@?

9ABCD@EF$G\]^o-pkq

_(!#"H$I

HBF4 ` HPF6 ` HTFSI( aFb (34GTo-rU1GXs

PRQS}~!c[<k46
$G



Grotthuss $

_&k_¦§OkPRQ¨6

®

KG-k±²º »  6I¼$HTFSIË$&\I<k4M$ÏÐ³´£$§

13Im)

#4s_s9kAT

4:5S7&$M
§$G³´£HTFSIIm<$(OPXQS6^Im(KGÑ)1kKlRm6C&0n$2v)xy&0z{|nO>

5=1Im HTFSI(Xm6A&N#4Im 587t9X

$F|<kvy!7

X¶Å9Æ4$1

W#j)iYZG[<­Xm

<G+TAH9¸¹Rm6CG5\=¤¥(Fµu!vFw

446587:9;1<CT5UVXW(Im)? 9kCnM

1£N2L_&2ImTFSI ÄJ!(Ì2Í$LOPXQSMn? 9kATn«¬134 nGÂÃXm:CH½^*\ dMghb
Y ZM[ \47stu!vwRW(120 ¡ 200 ¢§©$ª^

2Pef\<&k2(<v_k2u#v&w¯°±²\ 1&¸¹Xm6C&5·QFcFd

OPXQS:^*+,-./0213J!K<MLN2OPRQS(<m:CG587G$F!$GI2nOPXQS:$&%')(<_m6AnGr¾¿m6CGXW6YZ#cÀMÁH½MIJ¨¥Ç(F_4Îhi( ÖtsHIm ½(FÉRm:AD¼ ÈÊ1OPRQS}~_c[MnMÒÓ_4FD¼ËÊ§(\T§ mtOkPÔÕÁ<u!v w± ²
Gaussian98
Gaussian03
Hartree-Fock »Ø× HF/6-31G** Ùu!vFwGÚÛ2ÜFÝ( § TCG5L M<G+TA ?  <&Þ!B&zß2ÜFÝ)( §» (B3LYP/6-31G**)
TCCG5±²)àá_âäãåçæ è CG523¼¼ËÊkÊãåË±²IËÊ$DFT ±²
33

¼2

Ê
:ï

sîñ<&Þ!B&êkTMë@9ìË

$1\<Fð5yñ2ì)

32\1

sîñ

2

HM9kÅM9<kv4

ãòó

K$&õ

ö



C&5sHHFâ¨íXî9CGé<kv

DFT ±²Å9$GùW6YZG[ ùm:AT 471

Ë \ <nÒÓRm:C Ê

TFSI Ä<+kTkA $MéIJ!<ãå$Gýþÿ#(6ð5ï¼

Ë \ $
 Ê

DFT ±²13)ôñ_K$Gõ öï<øH93¼Å9kïPopulation

ñsIm-HIm ½ -TFSI Äs\(Im-HIm ½ )\sË \Ê
J!(GH9¼\a2
2HCNCH¼ Ês6nË\RsSüúGûýþ

1cCCCH$ãò<H) 1 2*+,-.#/0&123HMulliken
ãòFF

û

CF+$


<2  ú#4stîd

OSSFOF NCOH

 _4 Im sS³ ´£ § m:AT 4 N-HN-Hãò  ó Etãò  $(FëkA T5 ;CàMulliken Populationü ãòì)¨³ ´£ § m6AT 4µn; <GU!
 $ûâH  2 3!#"$&%'(µ<TAT 4v_xI J2(ùm6AT24:5
hºiN c[dHN<&­÷¿m6AT24:5$&IJ!K$ì4:5 IJ!(

3’H
2’ N C

H3O

¼b2 N

HaH

F

H

CN

C2 N

3C

H

3’HCb

H

1C

2’ NcNCHdH

4#4 3 ¼ Ê Ë \ <&+TAï 2 sSñ 3 v2 2+$GùW YZG[ \65 7<GUTMIJ!( sG4:5 7&$FI Jk1á 1 2?
 Population
Mulliken’sN-H
population( )n&Ó_4 Im sS³ ´£ § m:AT 4 N-H ãò s&d!c[ $ N-H ãò$ ãòó  ãò68 2<&Þ2B9 Më@9TM5F;C ³´£ §m6AT 4µU2
 $ N µ  <; â  TAT24tI JH (X m:ATT!7ks:n  ì465 7G$kv#xy< Im-HIm ½ 2 ¼  $U) < i h2nÒÓ)4 7 s<v â AkIkJ2<GÞ#B:(<;= _47 s6n1 BCG5¯³ ´£ §?>&@ \BA [(FC $ >&@ \BA [8sy2(6I¼E4MÆ!$ >@ \DA [$Mls$ ¿9 stE )4!s: 2 ¼   1
¼
 1
s
E= F 30.3 (kcal/mol) 3 
E= F 111.6 (kcal/mol)CG5&7G$ ãå ì)th $&ÒÓ2<kvAMknì   â?

¯2

9_47¼i
ìk465s6nG ¯ >&@ \BA [ Ea  HF ±² 1
sCG5M¥³!Ü

â(kcal/mol)
G ¯ >&@ \BA [ 0.3nHq)m6C#s
_ 9#4Gn à>@k1Ö § m:CnG\IA [2(KJ6LMN¿m:AT¯
DFT ±²(FÉXm6A4&Lå<uTA
¼

1$


3

à

4:5

3

¼



k1$OPXQS:N1O 2.5 P $FÿsEa

Ea=9.6 (kcal/mol)s¨íX9kC

b0.3857

1.1252c0.2789

1.5161d0.70221.0099

¼

â
1$



HF ±²ã

a0.5640

1.0409b0.4980

1.0574c0.2248

1.7389d0.6933

1.0087§ 3 ¨&©ª«6¬­ £¤ ¥¦ ¡®U ¡ ¢£¤ ¥¦ ¡ (deg.)¡ ¢ (deg.)

2C&5$<kv1.0117â1

3.9 (kcal/mol) DFT ±²0.7108

 2 3# Population
Mulliken’s
N-H
population( )
kOkPRQ¨6N2$

a  2N-1H-2’N2&
178.3
Ë \ $OkPRQS:N<kv2
¼3 Ê
164.6
Q2$&IJ!(FÌ2Í4 sï 3 $v 3&x<1&ðRm6Cµnhì#UT TVXW <3 4KiXH Im$µ< ãò m:AT 4tI J <Y
Z #47ks6ì â C&5 v
N 6Q!$GIkJé3 ª ¯  ãå $I J!(Mï<Fð5&R!
S < DFT ±²
3HF ±²OP¿Qî

A¥

N

³2Ü

(É#4stï$IJ

MIJk1T

[?\ HIm ½ < TFSI Ä n#4 st? 9OkPRQ¨$FNn)] 76<2EE k4s!29_465¯âstTxpÎ7ks<;1$ãå465F3ì)

¼

1

3C-2N-2’N-3’C
87.7
167.8

FFCFOOSSOFCHFH

1$OPRQ¨OFNHCHCC&] 72U^kT  IkJ u_vw¥ 6_6` (a¼m AT!4nh(+M¾ MC¼
k1OkPRQ¨F n)] 7i
13 q 3 HFr stu6vxwhyoz{|6<!EtT<:
m6C#s  465
$G  : ^_`¯Im/ HTFSI
2$b¼cÓ2b¼ ndT8s¨ ^  n&d Etfe < HTFSI 3}~ #t<  Imb¼ nd T8sS ^ 2kH q#4 stTxhgi ãå n3 4Mn_7:9  g#j $G lk1 TFSI$ m ¾#<kv â Aï 1 $ n  I J<  ï 2 $7 á I JknMD@Eoa ¼ ? 9kAT 47ks <&­÷¿m:ATÄ
4 sSð#p ? 9#4:5
2n2Im N

HNCCHX

HNNCH

H1) K.D. Kreuer, A. Fuchs, M. Ise, M. Spaeth, J. Maier,. Electrochem. Acta, 43, 1281 (1998).
2) A. Noda, M. A. B. H. Susan, K. Kudo, S. Mitsushima, K. Hayamizu, M. Watanabe, J. Phys. Chem.,B,107, 4024-4033 (2003).