1A16!"#$%&'()*+,$-./0 N-H1O=C 23
N-H1O-H 456789:-;<0=>?
@N-H:::O=CAB456789:CDE@(FGHI) JKL 9MNOP QRN;S T
UVWXYZN[\45]^_`abcd745eCfgh456ijkl-mnop[\45Cq
rstuvwxdC=>yCz{`|}~}0hN[\-xd_0#9:6C789:N-H1O=C456789:]#9:e745eC789:N-H1O-H45678
9:NC_uv`<0Bh456ijklCehw

NC[\N-p789:_~}0ooC¡¢h456ijkl£¤-¥¦o~}0p§NN-H1O=CN23N-H1O-H456789:`¨C456ijkl ©ª-4«o~N^C¬­]kl®¯°±²`³´<0µe¶·-¸o}¹º»i-./0789:C=>Nfg¼:½¾¿p789:`ÀÁÂ<0µe-Ã¿~N[\C789:`ÄÅÆhÇÈIÉ<0µe`Êr-<0^µNË=>N!"#$%e45-ÌÍ#9:`N-methyacetamide
C 1:1 )*+,$Ind-NMA1-»iÎ 4Ï`ÐloNÑ5ÂÒÓÔeÕÖ<0µe-Ã¿~N[\C×ØÆh789:Ù0N-H1O-HN23N-H1O=C456789:-}~³´opUÚXÛÜÝÞßàáâã-ÃbInd-NMA1
Ind-NH
3525)*+,$`[EoNÑäåæçxÏ5!

(a)Indole

è"ÂREMPI+)á%N!è"éêÎ(b)Ind-H2O1(c)Ind-NMA1 34916cm-1 exc.

3506

hole-burning+)á%`íîopïpÑ5Ind-NH3435

ëìàIR-dip+)á%N23IR-UV

3348
Ind-NHÂÒÓÔ(B3LYP/6-31++G**)`l}~)*+,$CðîñòNóô+)á%N2345(d)Ind-NMA1 34907cm-1 exc.

3509

69:õö%÷$-}~³´oNø _p

3309
Ind-NHðîñò-ùo~Natural bond orbital(NBO)Éú`û¿p)á%`^_$_%(c)23(d)-&<%(h)Ind-cNMA(in)ÀÑ\N23Ind-H2O1)*+,$CIR-dip+)á%`%(a)N23(b)-&<Ñ5ÂÒÓÔ

NInd-NMA1 )*+,$-.}~NN-H!&##

3200

!!##

3446

3298

(c)23(d)-Ù0'+)á%N^_$_C
óô()C*4¬­`Ø<ÕÖCp§NInd3491!\CIR-dip+

3464

eh¿p#ñò(g)Ind-cNMA(out)
3308

"3525

$-AþÿCñò !\w¥¦<0µew(f)Ind-tNMA(out)3314)á%`íîop9üNInd-NMA1)*+,3348

REMPI+)á%N23IR-UV hole-burning+

NMA-NH(e)Ind-tNMA(in)Ind-NHU 9 ü 2 3  ý X Ind-NMA1 ) * + , $ C

!%##

3300
3400
Wavenumber /cm-1!$##!"##

3500

3600

!1"#$%&'()*+,-.&/IR-dip-0+1'23456789:IR-0+1'

1O=C456789:`+Cðîñòwø _p^_ CIWIR+)á%`%(f)-(h)-&<µµNtNMA23cNMAN^_$_NMAwá*"+\N23,+\Ù0µe`&oN(in)23(out)N^_$_NMACCN9:w!"#$%45--ùo~N./01N232ûh3`Ø<IW+)á%eIR-dip+)á%CÕÖ`û4µeN% 1 C(c)e(d)`N^_$_Ind-tNMA(in)e
Ind-tNMA(out)-56op
Ind-H2O1)*+,$CNH78óôNIndÀÑ\CNH78óô-ùo~ 90cm-19à#,:áop;<-Çí¾_0^_-ùo~NInd- tNMA(in)N23Ind-tNMA(out))*+,$%(c)23(d)CNH78óôN^_$_ 177cm-1N23 218cm-19à#,:áop;<-Çí¾_0Ind- tNMA(in)N2
3Ind-tNMA(out))*+,$CNH78óôNInd-H2O1)*+,$C^_-ùo~N=A>CG?¾C
9à#,:á`&o~}0µCµeNInd-NMA1)*+,$CN-H1O=C456789:wNInd-H2O1)*+,$CN-H1O-H456789:Ãb¬}µe`&o~}0ïpNÓÔ-Ã¿~ø _pð
îñò-./09:õö%÷$NInd-(H2O)1)*+,$ 3.7kcal/molNInd-tNMA(in)eInd-tNMA(out)N^_$_ 5.8kcal/molN6.0kcal/molÙb%ANInd-(H2O)1)*+,$Ãb= 1.6 >G?}
µC9üN#)*+,$-./0789:op@A78óôB"#C9à#,:áCG?¾e(a)Ind-H2O
B.E. 3.7 kcal/molCDEdùFo~}0NBOGë%N789:A-H1B`NBC¹ºH5ùIJnQRNH*A-HCK9:!IJ *(A-H)( 2)[S Si ! j* =11.6 kcal/mol]

ELCHM)ô-Ã0H5C¶N¦Â-Ã0ðîÂeo~O0µCe?C¶N¦Â-Ã0ðî
Âõö%÷$NPQCRôõö%÷$ E¿~S§ _0wNE(2)i ! j*( 2)i ! j*-Ã(c)Ind-tNMA(out)B.E. 5.8kcal/mol(b)Ind-tNMA(out)B.E. 6.0 kcal/mol

NBC¹ºH5ùIJ

eA-HCK9:!IJ *(A-H)eCBhb*4YTÆ-ÕU<0%A-N#)*+,$C9:
õö%÷$NNBOÉú-Ã¿~ø_p E i(!2 ) j* õ

npRNH*

npRNH*2)[S Si(!
=8.29 kcal/mol]j*( 2)[S Si! j* =8.70 kcal/mol]nQRNH*

nQRNH*( 2)[SESi ! j* =5.37 kcal/mol]EE

ö%÷$N23IJCBhb`Ø<%`&<NBOÉúC9üNInd-NMA1)*+,$- 2 C¹ºH5ùIJnpenVw¥¦o~.bNPC¹( 2)[S Si ! j* =7.17 kcal/mol]

EºH5ùIJeK9:!IJwijklopP
B456789:np ! NH* e nV ! NH*wD
E¾_~}0µew4¿pWXNInd-H2O1)*+ , $   N n V ! NH* C E i(!2 ) j* õ ö % ÷ $!2"NBO;<=>?@ABCDEFGHIJKLMGHI/NOP

11.6kcal/mol-ùo~Nnp ! NH* C^_0.18kcal/molwY§~Z¾}µe N[-nVIJe
K9:!IJwijklopWB456789:nV ! NH*wDE¾_~}0µew4¿pµµNInd-H2O1 )*+,$Cn V ! NH*789:C E i(!2 ) j* õö%÷$-Õ\NInd-NMA1)*+,$Cnp ! NH* e nV ! NH*789:C# E i(!2 ) j* õö%÷$Z¾dh¿~}0wN^_ C(NInd-H2O1)*+,$-./0nV ! NH*789:C E i(!2 ) j* õö%÷$ÃbG?dh¿~}0µew40µCµeNInd-NMA1)*+,$NN-H:::O=CPB456789:wDE¾_0µe-Ã¿~NInd-H2O1)*+,$CN-H1O-H456789:Ãb¬}789:wDE¾_0µew4¿p