Download - Unit : kcal/mol
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
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Input structure
BOSO
45
46 — HOMO
47 — LUMO
Excitation : π→ π *
BOSO-twisted
44
45
46 ― HOMO
47 ― LUMO
48
49
Excitation : π→ π *