2A13!"#!$%&'()*+,-./01234567'89:;<=.>?1@AB
CDEFGHB IJKLMNOPQRNSKTN>UVB
WXYZ[89\]^_`abc'89\de.fg'hQijN,4k)ldm^nodpq
rZ[89dstruvw]dxyz{|_}~?1r9\^1 dZ[jNN.1NZ[89\'89\dejN.7?1'hQid\ZergZ1pNZ[89dwxyz{|_'hQid¢dpqrst£¤_¥.¦^r0^§rr

¡?1.jN¨©¨rNªdZ[jN«.E¬r­®¯_°±Z[89N²³d'89.`ab´^1¢\©N'hQ
idstrZN_µ¶tr·¸©¹©.?1¢\jº¨»¼½¾¿./01'hQid@AjNÀÁ¾./01ÂÃr'hQi_Ä5?1¢\.p
N'hQi_89ÅÆÇGÈ?1¢\_É.¨¬N¢^´d@AdÊgjN'hQi.pËÌ^1z{xyw'hQidÍÎxdpqr'hQidÏt£¤.Ð¸_Ñ°d \¢ÒNÓÔNZwier w JohnsonNKim dÕÇ-ÖN'hQid\Z_×c)*+,-Ø'89Ù2ÕÅ-ÚÛ4_ÜÝ¨ Þ. Zwier dÕÇ-ÖjNZ
[89\>ßdà!á&Qi_×c trans-Formanilide \'89\d¿|'hQi)*+,-.
/NN-H âNãä C=O â\'89\deËÌ^1'hQid\Z_åq'89dÙ2ÕÅ-ÚÛ4_æ¨¨©¨Nç´d\¢ÒN»¼½¾¿./N'89d>è

?1'hQidst£¤C'89Ù2ÕÅ-ÚÛ4éH.Ð¸_ÑÜÝêjëìr]¢í@AjN89Ø.!á&Qi°± Acetanilide (AA) \'89\d¿|Nãäîïðñ34)*+,- (AA-H2O1NãäAA-H2O1+) .½¾òó8ôõ_öÎ¨N÷95øùú\ûü?1¢\.pN'()*+,-dz{xy_ý{?1\\°.NAA d2345.åþÿ?1 C=O â© N-H â d'89Ù
2ÕÅ-ÚÛ4.>¨!"¨Acetanilide (AA)W#Y$%&'()#*+Ì^ AA-H2O1 d 1 ,-./0ô92345 ((1+1)RE2PI) +1)#ÇNIR-dip +1)#ÇN Photoionization Fragmentation Threshold +1)#ÇNãä0,-./2345 ((1+1’)RE2PI)Z¨ AA-H2O1+d IR-dip +1)#Ç_2{¨ ´N÷95øùú
(B3LYP/6-31++G**) _ÎN)*+,-dz{xy\3s+1)#Ç_ùú¨
WQ456YAA-H2O1 d (1+1)RE2PI +1)#Ç_2{¨Q4NAA 7÷[d 0-0 8;©207cm-1 Å)&Ú9#¨ 35697cm-1 .:;4&·2Ì^d.<N146cm-1 =Ç-Ú9#¨ 36050cm-1 .«.>;4&·2Ì^ u?.ÿr@^ ZEKE +1)#Çd2{©
N35697cm-1 .·2Ì^;4&jN
AA d NH â.'89Qi¨)*+,- (AA(NH)-H2O1)
d 0-0 ;4&.ABÌ^1(1+1)RE2PI +1)#Ç·2Ì^ 35697cm-1Nãä 36050cm-1d;4&_ÖC-=¨\¬.D^ IR-dip +1)#Ç_Eî.F? AA(NH)-H2O1Nãä AAd CO â.'89Qi¨)*+,-(AA(CO)-H2O1) dz{xy©D^1G¡ IR +1)#
Ç \  2 d + 1 ) # Ç _ û ü ¨  Q 4 N E î (b) ã ä (c) _ N ] ^ G ^ AA(NH)-H2O1 N ãäAA(CO)-H2O1 .AB¨ ¢¢NAA(NH)-H2O1 d NH(a) AA monomer-13472)&Ú9#¨1d.I¨NAA(CO)-H2O1 d'hQi¨ OH HÁ3sjN'89d!1 .ûJ 165cm-1(b) AA(NH)-H2O1 ( 35697cm-1 exc.)´NAA-H2O1 d2345.

ãä 5.9kcal/mol 1¢\8© pNS0 O3368cm-1 .·2Ì^;4&_9%-r NH HÁ3s2800;4&.AB¨ E0(b). AA(NH)-H2O1 d 0-0 ;4&_U®¨Z¨ AA-H2O1+d IR-dip +1)#Ç_3000

F? ´NE0d.NAA d NH â.'89Qi¨)*+,- (AA(NH)-H2O1+NEV)dz{xy©

33683743(b) AA-H2O1+
via AA(NH)-H2O1 0-0 ´NAA(CO)-H2O1+Z¨^§N3368cm-1_Ô.9%-r NH HÁ3s;4&·2Ì^1j`1NE0(c)d 3368cm-1 _Ô.j;4&ag·pNE0(c)d+1)#Ç°
bcdQ4©N3171

3622

3706

3212
3723
OH(!#)

AA(NH)-H2O1+ d+1)#Ç\T\]^d°d

37063624
OH(!")

 N  2 d + 1 ) # Ç j N E 0 (b)  · 2 Ì ^ 36223212(c) AA-H2O1+
via AA(CO)-H2O1 0-03152(AA(CO)-H2O1 ) Z?1\W[Ì^1 ¨©¨r

3171

NH(H-bond)Intensity+AA(NH)-H2O1+ . A B ¨ NH str.

E 0 (c) .

AA(CO)-H2O1 d 0-0 ; 4 & _ U ® ¨  Z  ¨ 2Ì^r3800(a) AA-Ar2+

W2Ì^1G¡+1)#Ç_F? XYdûü©NAA+ d CO â . '  Q i ¨  ) * + , -3492

3200 3400 3600
Wavenumber / cm-1!" AA#$%&'(AA-H2O1)IR-dip*+,-./01*+,-.

+

AA-H2O1+d IR-dip +1)#Ç_F? E0(c)dZiN

3720
OH(free)

B E 0 (a) . AA-Ar2+ d IR-dip + 1 ) # Ç _ F ?

3472
NH str.

3470
3446
OH(H-bond)>'hQi_Ë¨1¢\8©3718(c) AA(CO)-H2O1 ( 36050cm-1 exc.)

PjNAA(NH)-H2O1 \ûJ AA(CO)-H2O1 dTqE 0 (b) _ AA(NH)-H2O1+ . A B ¨ 3751
OH(!#)

AA(CO)-H2O1 dQiQRÇS-N]^G^ 3.8kcal/molN36443639
OH(!")

3417
3496

1¢\.pNS0 OP./01 AA(NH)-H2O1Nãä

X4NH str.

å^1ÈKZL AA+dM¨¬N_ý{?

IntensityÅ)&Ú9#¨1NH str.

HÁ3sjNAA 7÷[d NH HÁ3s©N55cm Å2800 3000 3200 3400 3600 3800
Wavenumber / cm-1
!7 AA-Ar2+/AA-H2O1+)IR-dip*+,-./AA(NH)-H2O1+)01*+,-.

AA(CO)-H2O1 d 0-0 ;4&_U®¨ AA-H2O1+_Z¨ZiN2345dejNAA+d CO âdÔf.'89gç¨1j`1N]deNAA+d CO â© NH â.
'89:;?1¢\8© S0 OPjNAA(CO)-H2O1dh>'hQi_Ë¨¢\_1\NAA d2345.åNNH âNãä CO âË?1'hQid¾I>¯N¿|OP\ûü¨ia.j:?1¢\N'89
:;?1S1\^1!2 AA(NH)-H2O1+)3456