4P097
Z-EN7-2,4-62?G?1H hydrogen-out-of-plane motion a),bÉmpÞ÷(Ù¹Oć¤Å 1ĒÁ«²± WPI-MANA2ĒJST ĈÈ Ï\ 1, 2Ēďæ Q 1Ēč _ 2,3 3)óL8>PKCM<Nm59B~}ĐRPSBđ M=C5NVÊåy,ē
11-cis RPSB * all-trans RPSB !bÉm íîg©´ĉĂëi/  Ð*-,ĐScheme1đēM=C5NV RPSB  11-cis ! all-trans bÉ
măqÃ 0.67 Ē¨g}ÂSÆÁĐphotorhodopsinđ 200 fs ąÆ-,[1,2]ēQ¥Ē¼»V 11-cis * all-trans !bÉm ăqÃ 0.15
+ĒkÃËbp [2]ē *7NA4ôV  Ē0*k­) RPSB bp `ý-,â*-,ēRPSB  C11!C12Íßt,µÜċlScheme 1Đhydrogen out-of-plane motion; HOOPđĒ¼»V)+7NA4ôV¥ 
1112,Y Ð*- +ĒÉmp1013/`ý,ëxQ,©,ēúĒKukura *[3] M=C5NV+
11-cis-RPSB N H
 11-cis ! all-trans RPSB bÉmþÔ/ð¬Ē×QjõÂĐS1đS ĒHOOP )ĒS1/S0 dĄ|[ (CI)hĀ +ĒjõÂS ½ÜĎhν® m õ Wē Ēß­/é],ÅóñÚ¿ēªÑÕ Ē11-cis ! all-trans RPSB  Scheme 2bÉmpþÔ HOOP )53Č/U, /ò",/ÌË24ēĒRPSB I;KÛEN+1 NH
27-2,4-62?G?1HĐPDI, Scheme2đZ-PDIHOOP ºÌĒPDI  S1 F:N5JK2@K3P§ċĐPESđñÚ/çēLys
1113+ Lys
N

1210H

all-trans-RPSBhν

53

1+42NH2E-PDIñÚ±ü¨āmĒpÞ÷ñÚ Gaussian 03 u#-, CASSCF ¸/Ççēactive space ĒPDI "ĊcÎĆ/âĒ6 Ċ 6 øÿē}Ć¤ 6-31G*/ÇēCASSCF ĊÎĆTö/ê&Ē GAMESS u # - , MRMP2 ñ Ú / ç  Ē CASSCF  2 @ K 3 P / ê ³  (MRMP2//CASSCF/6-31G*)ēMRMP2 ñÚÇoÀøÿ RÂ{ CASSCFĐsÂØĂ$đ/Çē ß ­  RPSB I;Kf (Z-PDI /u%) bÉmp Ētwo-mode
two-state I;Kè-,Y Ð*-,[4]ē#+ĒpĆ.,Â S1 S0 Â+ĒS1 ÂjõĒZĂßtßtnßtßt[£Đbond
alternation đ  , Ô  õ  * Ē C2!C3 # . +  w ù õ  , [4] ēMRMP2//CAS/6-31G*LDK¶& S1 minimum-energy-path (MEP) ñÚ I;
K/ä eÄ, (zĔ)ē
zĔÓ) C1!C2!C3!C4 ZċïĐ!1đ 60 ^Swù)( S1/S0 CI hĀ,ē H!C2!C3!H ZċïĐ!2: HOOP Î,đ 110Ô,ētrajectory ñÚ ' MEP ñÚ/p¦,ß­ *-,[4]ē ĒjõÂSĒ½ÜĎ® m ë+ĒpÞ÷Kukura *[3])¢¯-,pÞ÷ É,ē Ēbond alternationÝX¾ (Z-PDI*: zĔ 1.8120
Bohr amu1/2 ¾Î) *Ē!1100
0.7 Bohr amuĆ¤Ē±üàv S1PES /¡  S1 MEP  É,80
θ = 0ºpÞ÷ ì ,ē
2.2 Bohr amu
θ = 5.7º
1.8 Bohr amu
Z-PDI* *&Ē!1 Ć¤60
0. Bohr amuñÚ S1/S0 áûÖą/u40
θ = 67.2º% S1 PES /ñÚß­/z 2 Óēz 2  PES ·Wë
20
7.1 Bohr amuZċïm/z 3 Óēz 2S0 CAS
S1 CAS0*Ē!1 = 40° S1/S0 áûÖą
S0 MRMP2S1 MRMP2hĀ, . ,ē Ē-20
01234
5678z 3 *!2 = 127.6°+Ē!1 
Reaction Coordinate / Bohr amu1/2
ĒHOOP /è!2 zĔėMRMP2//CAS/6-31G*), S1 minimum-energy-pathċ *-,ē(MEP)ē0.7 Bohr amu1/2 ]ú°ē1.8 Bohr amu1/2 ]ú*ĒÒ Ēaç HOOP l bond alternation ßwù #,ē!1=67° S1/S0 á) CI hĀrã+Ē ûÖąhĀē
250
HOOP Émp/`ý
C2-C3-C4-C5
N-C1-C2-C3,,[5].
Energy / kcal mol -1

1/2

1/2

11/2

11/2

1Energy / kacl mol-1160

S0 CAS
S1 CAS
S1/S0 CAS
S0 MRMP2
S1 MRMP2
S2 MEMP2

Z-PDI*

140
120
100

DPC4080

Dihedral angle / degree

1/2

LEDP

60

H-C2-C3-H (θ2)

200

150

100

50

40
20
00020

4060

80

100

θ1 / degree

120140160zĕė±üàv !1 Ć¤¡ PESē!1=40°áû¾(DPC40)hĀ,ē180

020

40

60

80

100120140160180

θ1 / degreezĖėzĕ PES Zċï±üm
HOOP
H-C2-C3-H (!2) Î,ē

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