1P056
CH3NCO ! H2O, NH3 !"#$%&'()*+,-./0!123456789:;!"#$%& 1'"#$(%& 2)*+, -. 1%/0 12 2%34 56 2%78 9 1<=>?:;<=>?!RN=C=O)@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\'CD]^V_`abcdWeHfghijklkmnopqCDbrstPuv
wxyzk{|@}Q`j~@:;<=>?!CH3NCO) NH3 bmnopv
?Zyzka?vk'bmnZk{F'{opb^@ NH3 bAB v¡¢hiWbZ@Ql£{j¤¥@ CH3NCO/H2Ob¦V_`aWS§v¨`'CH3NCO  H2O, NH3 b©ª«TV_`a'?
¬n­®¯V°\±²k{j<@AB8C56? CH3NCO @ CH3COCl  NaN3 lNPk{Wbv³´kaµTk{jCH3NCO  H2O ¶{@ NH3 v·¸ Ar Z¹ºk'»¬v¼½kQF 20–25 K V¾¿k{ CsI ÀÁÂÃÄVÅÆÇÈ{j·bÉ 10 K VÊvËÌ'Nicolet Magna 750 vT`a FTIR?vk{jÍÎ>Ï°Ðopb^ÑÒ­¼ÓÔ®¯@ Gaussian 03 v
T`a¨£{j¶{'Atoms in Molecules!AIM)6VÕÖH×nØÊÙÚ@ AIMPAC v'
Natural Bond Orbital!NBO)ÙÚ@ GAMESS VÛÜÝÞß NBO 5.G v·¸µTk{jàab®¯@"#$áâ6ãLK>b Altix 3700 ÁZ¨£{j<DE!FG?CH3NCO/Ar  H2O/Ar vÃÄVÅÆÇÈ FTIR ?vhi'CH3NCO/Ar äåZ@æçVèl£{`H_lbéêbëÊF@£Æ\ì$k{jÅÆÇÈÄbÕÀÊvGHhiëÊì$@°\íîQijïbéêbðÞR@ CH3NCOÍÎ>bñòVó{F'H2O bôõö÷øùZ@qq$ÆH úÔ<û?k{3586.7 cm!1!"# = !51.6 cm!1)VÜ{jüývþÿ{S§l'ïbéê@àaÃ.
b­ bWbZ[\'PmÍÎ>îkH!QiéêFQ`ïq"Êb#l'
CH3NCO–H2O 1:1 opV$%hi±ÿij
tPk{opb^V_`a&'vi{('CH3NCO–H2O 1:1 opb^ÑÒ­v
B3LYP/6-311++G(2d,2p)J)Z¨£{ï*'H2O b H F CH3NCO b N +nV,`{ Type N
 O +nV,`{ Type O b- .b/01^FA¶£{jFig. 1 V·b^v¡hjï@ CH3NCO–NH3 opb^.2ka`iF'H2O b H  CH3NCO b N ¶{@ O (a)(b)Type N

Type OOO
2.771 Å150.3°"E = !6.57 kJ/mol(!6.60 kJ/mol)*"E = !8.60 kJ/mol(!7.63 kJ/mol)**BSSE corrected

2.156 Å130.4°
2.815 Å101.1°

129.9°

2.311 Å
91.2°

NCO

C

CO

C
N

Fig. 1 Optimized geometry of the CH3NCO–H2O complexes at the B3LYP/6-311++G(2d,2p) level.

b34@ôDhi NH3 op°\5H'6 Table Frequency shifts of the CH3NCO complexes.
ExperimentalCalculated a)
V Type N Z·b7,Fîk`j89#
Assignment"#"#
:;<>v=>k{opOPV°i #monomer #complex
Type N Type O&&&&1  ­ : ;  < > @ ·  ¸  !6.57, CH3NCO–H2O
3638.33586.7
OH str!51.6 & !68.6 !27.2!8.60 kJ/mol Z Type O b?F1Z[i 2292.7
2283.9NCO str!8.8 & !16.7'0.1
CH3 rock1136.3'1.1 & '5.4!1.4
F'NH3 opb@N°\·bA@BC`j 1135.2
856.8
862.9
CN str'6.1 & !2.2!1.3
D^Z®¯k{¼ÓÔbopOP
577.1581.9
NCO def'4.8 & '1.9!4.9
V°i<û?"# vSEFG!Table) CH3NCO–NH3&&&&NCO str
2285.6!7.1 & !7.6!7.1
hi'EUV@ Type N b?F°Hô 2292.71449.4
1444.9CH3 def!4.5 & !2.6!4.6
Dhij1­:;<>b$ÆC@H 1422.0
CH3 def
1413.6!8.4 & !7.5!9.0
1124.5
CH3 rock!10.7 & '8.4!7.3
IhiF'?rZ@ Type N o 1135.2
974.5
1015.7NH3 def'41.2 & '23.1 '43.3
pFOPk{±ÿijNH3 opb@856.8863.6
CN str'6.8 & !7.0'0.3
NV@:;<>'Ô<û?`Jl
NCO def577.1581.7'4.6 & '0.6!2.8a)
B3LYP/6-311++G(2d,2p), scaled.
W Type O opbtPF¡¢C{jH2O Ï°Ð NH3 opVÏÈiMNbfgvK(a) CH3NCO!H2O, Type N
Lhi{(V'B3LYP/6-311++G(2d,2p) J)b×nØÊ!$)V°\ AIM ÙÚv¨£{MFig. 2
V Type N opb%2$ bNGO'bond path!BP,OH)Ï°Ð critical point!CP)v¡hjH2O op
Z@ H2O b H  CH3NCO b N bsVklm
nsb BP  bond CP!BCP, P)FfgkQ`j.?'NH3 opZ@ NH3 b H, N  CH3NCO bOCNN, H bsV·¸ BP  BCP FfgkaÏC\'rQV ring CP!RCP, R)W[£aST^2v¡hjUbNGOZ¡k{% $ FVbøù@×nØÊb/0UWrvXhF'NH3 b lonepair VôDka CH3 ÕYÂZ\[k'0\MNOPV]^ka`ijQÏ'H2O, NH3 `Jb(b) CH3NCO!NH3, Type N@NZW Type O @STb0\MNopZ[£{jH2O opZ@ Type O b?F CH···O 34F_`VWll`J BCP Ffgk{jopVÏÈi©ª«TbEav6Ùhi{('NNatural Energy Decomposition Analysis!NEDA)v¨`'©ª«T:;<>vmbk{j`JbopZWc×dÏ°ÐmedV°i]^F$Æ`F'H2O opZ@ NH3 opVFf×ghOCN
dF$ÆH'Type N Z6VíîZ[ijïC@ïbopZ OH···N 34F5HS^vOPkQ`ïijF[ik`ij
lÁ°\'CH3NCO @ N, O mmZ H nop
ka'CH3 mmZ H p^pkaqHF'©
#mnb H p^EFìh H norb©ª«TFig. 2 %2$, CP and BP of the CH3NCO complexes atFstUVQi±ÿij
the B3LYP/6-311++G(2d,2p) level.