1P040
 ʰ!" #$%&'()*+,-./-01234567(89:;/<=>%&'(?@ABCD67EFGHIJ( +,-./- OHKLMNO

PQ645 01R%ST'()* UVWBXYZ%_`a)[1], [2]45[\/N?b "Dc 45'(d(D)d(A)]^WBXefZ 45[\/N% dDaDDAdAaA(d agJhJDiajA6k'( l)mn'(?e) gJhJ [\/N6op(DAq 45rs tuaF rsvXMOH = − dD + aD +dA − aA%$w(?a)xEF  45[\/NFree(yz) 45rsx{w|6MOH = −2 −1 0 1 2 3 48}~6BpJ(?45[\/N dDaDDAdAaA67(mn<\[1]+L6%Figure 16'?bJec b "D%$wFAr:9<op(\/-[2]%EF)?cd 6'(x  OHKLMNO9N67ZPQxc(?gbcd 

uncoupled OHKLMNO%Ha)?e)X6owFi <\  @APQ%uncoupled¡¢cw£H¤¥¦a)?£H MNObci69N

3wc£¨'(S©J(45[\/N%ª«(bxc(?I6§l%¥¦'(¬­®¯°-%$wF X67EF±J)45²8-³/%MOH´µ¶p)?

£·"DX Gaussian 03 ¸¹%$w ºs»´lD(B3LYP/6-311++G**)

c 22 }~ <\ =>¼½o7¾ @APQ%E)? @APQ a)OH ¿À ÁX%ÂF¬ÁXc1ÃdÄÅaFw uncoupled OH ¯/O §l¤%±)?±J) @A §l¤νharm ÆνOH = νharm(1.184 − 0.00006νharm)%$wFÇ/Na£H MNO¥¦a)?e) <\ 45²8-³/∆Ehb %¿7È6ÉÊiE)?
(1)∆Ehb = nE (monomer) − E (n − mer)E(monomer) E(n−mer)Ëdo7¾ n d Â²8-³/c(?rsvX MOH 6B~IJ(45[\/N 45²8-³/%∆E(MOH)o <\ 45²8-³/x∆E(MOH)ÌÍÎcmIJ(Ï'(?
∆E hb = ∑ nM OH ∆E ( M OH )(2)

M OHbbc ∆Ehb (1)Æ7ZÐ*)¤cZ nMOH

<\ 6owF MOH 6®ÑIJ(45HO H

HO Hlc(?(2)Æ ´Ò%$w ¬­®¯°-67Z∆E(MOH)(0 < MOH < 4)ÀÔ<:-

11DA21 aD

dD

H

O H

aD

HdA

O H

aA
12DA21 dA

H

O H

H

O H

02DA21 ¤%Óa)?

H2O / D2O(0.5 : 99.5)Õ5Ö%ª×a BRUKER FT/IR IFS 66 V/S(ØÙÚ: DTGS)%$wF ÛÜD(ÝÞ: CaF2)cHa)?ß- àsá# Ô-âãäAåàs.N:¸/67Zæça)(10 °Cè65 °C)?

4éSêFigure 2(a)6 @APQ67HO H

HO H

12DA11 HO H

HO H

12DA10 

HO H

HO H

12DA20 Figure 1. Examples of the hydrogen-bonding patterns
represented by dDaDDAdAaA. The number in circle
corresponds to the MOH value.

3800

45ìí6kaF¸9:a)4é%'?1î MOH 6®ÑIJ(νOH~ïa)§lðñ6òJ

MOH

óô6õwö§l÷6ø

ù:'(bxfúE)?e) Figure 2(b)6¬­®¯°-67Z±J)∆E(MOH)% MOH 6kaF¸9:a)4é%

%6É()*∆Aν,i = Aν(Ti) − Aν(Ti+1)%a)?bbc Aν(Ti)às Ti 6op(§lν
gCsc(?

4é% Figure 3(B)6'?Âàsðñ6owF MOH = 26®ÑIJ( 3360 cm ¶−1x3530 cm−1 ¶ xóôaFoZ ∆AiúE)?Ü 67Z d 6owFBXx 4 Ã 45%ÍaFw(S©JFw(xbJ 12DA21
MOH = 23530

45[\/N(Figure 1 )6këa

MNOrs%©(?aúa Figure 3(A1)6'

2015
10MNOrs%©( 11DA21J((Figure 1 )?e)à6õw FreeOH xóô'((Figure 3(A1)))* ü ðñ7È3 MOH = 2[\/NMOH = 1óôxÉJ(Pí67EFrw45[\S©J(?bJ ∆E(MOH) ¤úBú(7È645/Nú{w45[\/NbEFw()*S©J(?
S

A(10) − A(15)

=x

3548

(A2)

0.4

A(60) − A(65)

10 ºC
65 ºC

0.2

0.4

0.2

0

Absorbance / a.u.

[\/Nxþ¨aFw(S©(A1)
Absorbance / a.u.

YZ6 MOH = 1

MNOrs

4

∆A i

6owFPía)

c Figure 3(B)36owF45xP

d

+ 12DA112
MOH3350(B)ía)iþ¨aFw(bxBú(?a)
xEF

1Figure 2. (a) Relationship between the νOHwavenumbers and rOH for water clusters.
(b) The hydrogen-bonding energy of thehydrogen-bonding pattern with MOH,
∆E(MOH), plotted against the MOH index.

®ÑIJ(MNOxGHIJFw(bú
89:;/<1.01(b)0ü ðñc 45%ÍaF3w Free 6

£

125

MOH = 1 6®ÑIJ(§Í63

3

0.95 0.96 0.97 0.98 0.99
rOH / 10−10m∆E (MOH) / kJ·mol −1O

23000

/<:

§l÷xóôaFw(bxfú(?às6õÈMN

13200

Figure 3(A2)6  üðñ6op( uncoupled OH KL9x§løù:a)?e)ö§l÷ krsxö a−103400)?

àsýþR%a)?àÜ6owF

free
MOH = −1
MOH = 0
MOH = 1
MOH = 2
MOH = 3
MOH = 4free

4óô6õw45²8-³/xóô'(bxûú*J g óô MOH 6kaFÌÍ2c(bxBúE

MNO

(a)

3369

'?MOH3600§l3524§l¤% kë'( OHν OH / cm−1Z±J)νOH07200 7000

3600
3400
3200
Wavenumber / cm−1

3000Figure 3. (A1) Temperature dependence of the uncoupled
OH stretching band in 7250 – 6900 cm−1 region (A2) thatin 3700 – 3100 cm−1 region for the H2O / D2O mixture. (B)∆A spectra calculated from the IR spectra displayed in(A2).

[1] K. Ohno, M. Okimura, N. Akai, Y. Katsumto, Phys. Chem. Chem. Phys., 2005, 7, 3005.
[2] K. Ohno, T. Shimoaka, N. Akai, Y. Katsumto, J. Phys. Chem. A, 2008, 112, 7342.