   ! " #$ % & ' ( ) ( ' *+ , -*+,#-c /.#0#132:<;>=@?ABDCFEhji(PB) `aniline k (HOMO) lnm
pqsrutvwyxz#{g)o!

#t

Scheme1probe(PP) >#
|'
U5
300fs  g
¹ASd)ef_g

Zj|}n~X_g)


de>f

Z|hX)omjlme#fOR(O1-C2)

S1 abck (LUMO)
quinoneimine
Na, b OZpump200 LuMNhν

ϕ(C4-C5-N8-C9))

R(C5-N8)ϕ(C5-N8-C9-C10))NN

R(N8-C9)ab Z 1) 8tJ¡¢£x %lnm6`
m
X#g>?A BDC¤EG>HJI#KNj¥¦#§©¨#ª%ef «¬Agc !#"%$&')(7 89a, bNO)PQ RSUTWVX|

CREST-JST b a, b 546.

G>HJIKL6M

A_^A

YZ[\]a R(C12-N15)­NS3®¯°±²
N

Scheme 1g³

»  xt def½>S%o  efZ  ab ¾j¿%À ÁÄÅÆ Ç)È
`3Ã
#
ab initio ÉÊ©ËÌ%Í%Î%ÏÐ)ÑÒ>ÓÕÔÖ×)ØÙÚÛÝÜßÞà_áJâ PBããuçèéêã6ëì%í)î)ïð6ñòyóJô3õÔÕö÷ø>ùúSå)ÿ æ
û<ü%1ý ä)þ©
ü%ýãÇ ã üý Ç×Ôuú×ÙÚÛù úèéãÜâÔ referenceä)å üý state-averaged (SA2-)CASSCF(2elec,2orb)
ãÇÔ6úØ
MS-CAS(2,2)PT2TDDFT(B3LYP)
SAC-CIü%ý
ÇÈÈÇÔuú6-31G* ÔÖ× 6ú
MP2/6-31G*ãÔ Ö× 6úã
Üâ S1 Franck Condon (FC) ä)å
minimum energy path (MEP) SA2-CASSCF(2,2)/6-31G(+d onüýÇÔuúO and N atoms),#ºj»6¼¡¥o·¸r)´µ¶
H3E%Âg³N     "!
#$'%)&+(*,.-/01    $4235


7"6

89

:,.C"- DE 1$$'243  ";"<>=@?
 A B243
 * (.FG$243
(IH S /S$ conicalintersection (CI) minimum (S /S CImin) SA2-CASSCF(2,2)/6-31G(+d on O and N'CDEatoms) 243
 S FC 7FJG 5abinitio(LKMN O trajectory Tully fewest switching (TFS) algorithm P 1
surface hopping
hopping algorithm
WV Ab initio Q !#$%'& V SA2-CASSCF(2,2)/6-31G(+d RSTUon O and N atoms)
1 X RSY[Z 1]\^ Molpro2002, Molcas6, Gaussian03    "!#$%'&_( Table 1  \^ 3`@ab` Jc max 'de Zgfh7 i 1 ÜâÜ1âÜ1Çãä)å

16úÈü%ýû0ÔÑ#ÔÖ×)Ø
üýÍ ä%å%Î

ÈÉÊ©ËÌ%Í%ÎÏÐÈÈÖ×üýèéãü%ýÈ2)ÔÖ

6ú6úÔâÉÊ©ËÌ)ÍÎ%ÏÐÔÖ×üýâ#þÜ0uúuúÔÇ)á

ããuúa)

Table 1: Calculated and experimental vertical excitation energies (eV) of phenol blue
SA2-CASSCF
(2,2)
3.35

State
S1(HOMO LUMO)
S2(n(O) LUMO)

MS-CAS(2,2)
PT2
2.17a)TDDFT(B3LYP)
2.26
2.52

SAC-CI(level2)
2.35
2.70Expt.b)
2.16

6-31G* basis was used. The geometry was optimized at the MP2/6-31G*level.
Ref.1. λmax in benzene.
ãèéÇÈ×ùù HOMO LUMO ä)å)æ
SA2-CASSCF
ionic state ÇÔ
×#ù Ø MS-CASPT2ÎÍÔø_ùØÇ ã×Ø%á
×
TDDFT(B3LYP) SAC-CImaxã ÇãÈÇÒ
×#ùÜØÔ
×Ò3×Ò×â úmax>ã üýããè#é ÈÇÈØ TDDFTSAC-CIlone pairn LUMOèéèéèéØ HOMO LUMOHOMO LUMO
0.3eV(S1) ä$ .j.kljm !#$b%n& "o 24p 3  q0r 0 G .'s
 j>t O Q ub= vw >Zyxbsz"{ 1| 1 243 $ ^ Z4} \1 ^ s ~ G 7 t  6"'d"3e`a` c . Z' }cxZ " '" vw \^   n
Z 8"96 ,b- j>t 253 $F[G@1  t"Us C"
 " .Z5s@".
* S FC 7FJG MEP ( Figure 1  \^ 5i 1  S FC   1  MEP barrierless " 46 MEP n @A B E ' 7Z MEP RSCI   Zs GF.¡ S /S R(O1-C2),s'¢ k R(N8-C9), R(C12-N15)s'£ k t S16  1 Scheme 1¤  i 1  jJm R(C5-N8)
§¦ ª«s'¬"² p >.Z ­.® bk
7K*y¥"¦ [*°¯0`± As'B p >VBk  ¨E ©n1 A B ϕ(C4-C5-N8-C9)Zp MEP
10³ FJG 90³b)ÒåÜ×#ùâ110ÇãÕê6úãä)å

ùæÇÈÒÒüýñãÔuúÈÔä)å

1ØuúÒãØ)ø_ùÈØ1 ä)åø ù>ÇÈãØuÔæ

×#ùúæ××Ü Wâ111.35

10Ôá

180.0

æ

06ú0Ü

ô

1.40

S1 FCÇ

ù

â

01Ô

ú

1

ã

0

S1 energy
S0 energyR(O1-C2)
R(N8-C9)
R(C5-N8)
R(C12-N15)
ϕ(C5-N8-C9-C10)
ϕ(C4-C5-N8-C9)

40.0

_ù

20.0

È

0.0

ã

060.0

Energy (kcal/mol)ÈötowardS1/S0 CI

1.30

1.25

Bond length (Angstrom)

Ø1.20

0.0

0.2

0.40.690807060
504030Dihedral angle (degree)E 1 /  ´ 1 ϕ(C5-N8-C9-C10)² 40³ FG 0³ Zg E 1 S /S CIZ4}"  . (IH S /S1 CImin Figure2  S /S CIminµ¶Z  branching plane gradientdifference (GD) Z derivative coupling (DC)3 ¸·¹$ 7º G $. ¯ » ¯ W¼  ½
Z S /S CImin A B
S /S ¾¿ `0À Á1¶i  S /S CImin AÂBϕ(C4-C5-N8-C9)=73.8 ³, ϕ(C5-N8-C9Figure 1 ù S FC ú0ûübý4þ MEP ÿC10)=-0.3³
quinoneimine ÃZ aniline ÃOsÄÅ' WZ " . Zs'ÆÇ  >6 branching plane ¼ ¾¿ `ÀÁ $ ¯ È .FG  CImin DC ÉbÊ sloped Ë CI  .Zs@i47

201000.8

MEP (au [mass-weighted / sqrt(total mass)])

Ç

Ç

×#ùã

È

ã

ùú
Ç

ù

-0.02
0.00-1.0

0.5 *bohr]
mu-0.04

0.0

0.02
0.04

-2.0

-0.04

-0.02

0.00

0.02

GD' [al]Energy [kcal/mo1.0

ϕ(C4-C5-N8-C9)=73.8
ϕ(C5-N8-C9-C10)=-0.3

S1/S0 CImin

S0äuú

S12.0ã0.04

ù S /S CImin  branching plane  S /S  !#"$ $ÍÌ SS /SFCCImin.Fþ %G & ab(')initio( RSÎÏZ 1 'RSTU V XRSY !#$%n& V S FC   1  TFS trajectory ? Ð G h7¼  Figure35.
6
 i 1  S FC   1 > trajectory ² 110fs surface switch 1 ÑÒ S FJG SÖ×ØnÙ } ÚÛ1  W \^ PP oÜ ÝnÞ e×  j}Õ S0Ó"Ô 1 200fsC  ã nä PP ß7à'á"â
1 £ b
200 å 300fs 8æ. çde Ñ 7èt8 .æ>í1
_Ö7×.é PBØ }"ê Õ u "ë; ì <"îïsð k  ò  ZvWñ G  1
6  A7B
ê E =S FC .FG S
\^ Z 0ó@ôÓÔn6MEPõ Ê  S ÓÔ 1 
 i 1  trajectory  = 1
Figure3 ù S FC ú0ûü>ýþ ab initio *+-,. /0 12
Figure3öktÿ )3  TFS trajectory G @÷ pϕ(C4-C5-N8-C9)k "s ø õ Ê trajectory 576  ~ G 7ϕ(C5-N8-C9-C10)  Gãä)å

ÇØä)åæÇãùãÔä)å

1ÉÊ©ËÌ)ÍÎ%ÏÐü%ýÔä)å

16úùã ã

101â

0×Ç

ã

Ø3Þàjáã%Ö

ãÜÒùÕúä)å

1ÇÈø>ùÇâã)×>ù
ã)Ø

ÈüýùJúäå6úØøÒã

È%Î
Ô101)

1.00ãØuéÇãS1 FCÇáÄÇÌ×ÈÔã0 ä)å

0ÜÇÈSurfaceSwitchã

-40

1401200.8100

S1 population
S0 population
S1 energy
S0 energy
Trajectoryϕ(C5-N8-C9-C10)
ϕ(C4-C5-N8-C9)-20Energy (kcal/mol)

1!

10.5 *bohr]

0.6

0.4-60Population

D C' [am uFigure2

80
60
40
200.2

üý0 äåæ

00 ä%å)æ

-80

0.0

#Ò
ê

0100

150

200

Time (fs)

ÈÈ

Ò

È

50-20

Ò

1ØØ

Ø

ãã

Ç

×#ùú

References: 1) Y. Nagasawa, et al. J. Mol. Liquids 90, 295 (2001). 2) J.C. Tully, J. Chem. Phys., 93, 1061

(1990).

Dihedral angle (degree)ÒãØ1