Unit : kcal/mol

S1

0 (0)

106

T1

S0

25(20)

45(42)

S0: CASSCF at B3LYP geom. (B3LYP Opt energy)T1, S1: CASSCF at CIS geomBasis set: 6-31+G(d,p) CASSCF(14,12)

108

92

95

88

109

8792

103

64

90

64

71

87 84

69

73

69

107(vertical from S0)

S1

CIS TD(SP) CASSCF(6,8)

CASPT2(6,8)

BOSO 0 0 0 0

ts3 10 -4 4 -19

tau -1 -8 -23 -22

ts2 4 -15 -34 -28

ts2_R 2 1 -44 -39

ts5 2 0 -45 -37

twisted 2 -3 -39 -36

ts6 8 -31 -27 -22

trans 5 -28 -18 -16

CIS TD(OPT) CASSCF CASPT2(6,8)

BOSO 0 0 0 0

PTTS 10 0 2

BOSO-t-cis -1 -5 -22 -17

irts-1 4 -3 -55 -15

tautomer twisted 2 13 -67 -1

irts-2 8 3 -51 5

BOSO-t-trans 5 4 -38 -6

1.Theory ->EOM-CCSD/6-31G(d)2.Basis set -> TD B3LYP/6-311+G(d,p)3.orbital

CIS TD(SP)

53 A’ A’

52 A’ A’

51 A’ A’

50 A’ A”

49 A’ A”

48 A’ A’

47 A” A”

46 A” A”

45 A” A”

44 A” A’

43 A” A”

orbitalCIS TD(SP)

BOSO Cs 46→47 A”

46 →48, 46 →51, 46 →52

ts3 Cs 46 → 47 A”

44 →47

tau Cs 46 →47 A”

46 →48, 46 →50

ts2 C1 45 →47,46 →47 45 →47, 46 →47

ts2_R C1 45 →47,46 →47, 46 →48 46 →48

ts5 C1 45 →47, 46 →47, 46 →48 46 →48

twisted C1 45 →47, 46 →47 44 →47, 46 →48, 46 →49

ts6 C1 45 →48, 46 →48 45 →47, 46 →47

trans C1 46 →47, 46 →48 45 →47, 46 →47

Unit : kcal/mol

S1

0 (0)

98[87]

T1BOSO63(57)

ts267(74)

tau65(57)

trans68(63)ts1

88(63)

S0

25(20)

45(42)

S0, T1: CASSCF at B3LYP geom. (B3LYP Opt energy)S1: CASSCF at CIS geom [TD-B3LYP SP energy]Basis set: 6-31+G(d,p) CASSCF(14,12)

99[86]

85[82]79[78]

89[117]83[116]

90[119]

106[85]

113[88]

103[91](vertical from S0)

Unit : kcal/mol

S1

0 (0)

106

T1

S0

25(20)

45(42)

S0: CASSCF at B3LYP geom. (B3LYP Opt energy)T1, S1: CASSCF at CIS geomBasis set: 6-31+G(d,p) CASSCF(14,12)

108

92

95

88

109

8792

103

64

90

64

71

87 84

69

73

69

107(vertical from S0)

B3LYP/6-31+G**Unit : kcal/mol

S1

TD B3LYP(SP)

0.00[0.00]

87.25(0)

T1BOSO57.34

ts274.30

tau56.50

trans62.94ts1

63.14

S0

19.84[25.21]

41.96[45.36]

[CASSCF] CASSCF(14,12)

88.20(-0.95)

86.07(-1.18)82.14(-5.11) 78.36(-8.89)

119.34(32.09)

84.81(-2.44)

117.07(29.82)

116.39(29.14)

First excited stateUnit : kcal/mol

CIS(S0→S1, SP)

110.84(0)

118.59(7.76)

TD B3LYP81.60(0)

BOSO103.37(0)

[0]

tau.102.14(-1.23)

[-14.04]

ts2107.68(4.31)

[-11.25]

twisted105.34(1.97

)[-19.10]

ts3113.15(9.78)

[2.21]

115.28(4.44)

CIS(OPT)

ts5105.59(2.21)

[2.54]ts2_R

105.56(2.19)[-18.65]

trans108.76(5.39)*

[-3.48]

ts6110.94(7.56)*

[-14.12]

81.55(-0.05)

[CASSCF(SP)]

CASSCF(14,12)

76.81(-4.79)

Molpro-quickstart

• Profile– Born-Oppenheimer approximation– Approximate calculation– Multireference methods

• Input structure

• Profile

– Born-Oppenheimer approximation– 假設電子和原子核為獨立運動 ,彼此座標間沒有相關 , 只處理電子波涵數

– Approximate calculation

• 1.

• 2.

– Multireference methods

Molpro-quickstart

...321

...2_)2()2(

)1()1(32

11

111 cionconfiguratcc

eee EH ˆ→Schrödinger eq.

Zeroth order aproximation limitation

Single ref. Hartree-Fock determinant 1. Bond dissociation

2. Electron excitation

3. Degenerate state

Multi. ref. Multiconfiguration self consistent field, MCSCF

! 後為說明項, 表示到下一個步驟; 表示指令終止

Cartesian coordinate,default :bohr

Default : spherical harmonics (5d,7f etc)

占滿軌域 51個 ,其中有 38個是 A對稱 ,13 個是 A〞對稱不作躍遷的軌域有 39個 ,其中有 38個是 A對稱 ,1個是 A〞對稱SYM=1 表示 Cs對稱 ,State,2 表示計算基態與第一激發態

*** 表示檔案開始

--- 表示檔案結束

Input structure

BOSO

45

46 — HOMO

47 — LUMO

Excitation : π→ π ＊

BOSO-twisted

44

45

46 ― HOMO

47 ― LUMO

48

49

Excitation : π→ π ＊