kirin
DESCRIPTION
Kirin. 2012/11/30. reaction pathways at different methods. reaction pathways in singlet ground state at different methods. There are no tautomer_trans_in forms in the singlet ground state at differenet methods. r eaction pathways in triplet ground state at different methods. - PowerPoint PPT PresentationTRANSCRIPT
Kirin
2012/11/30
N
O
OHhv
ESIPTN
O
OH
trans-cis isomerization?
N
O
O
H
2reaction pathways at different methods
54.2(0.0)
72.6(18.4)
53.1(-1.1) 54.2(0.0)
70.2(16.6) 65.3(11.1)
96.5(0.0) 90.6(-5.9) 87.3(-9.2) 94.0(-2.5)
71.3(-25.2)
96.3(-0.2)
88.4(-8.1)
B3LYP/6-311+G** S0TD-B3LYP/6-311+G** SP S1, S2B3LYP/6-311+G** T1 pathway 1B3LYP/6-311+G** T1 pathway 2
S0
S1,or S2
T1
normal form
TS
tautomer_trans_out
tautomer_cis
tautomer_trans_in
TS
tautomer_trans_outtautomer_cis
tautomer_cis
TS1 TS2 TS3
normal formtautomer_trans_in
tautomer_int
without parentheses : relative to singlet state normal form
unit: kcal/mol
3reaction pathways in singlet ground state at
different methods
• There are no tautomer_trans_in forms in the singlet ground state at differenet methods.
19.1
0.0
35.0
28.4
39.5
31.7
68.3
39.8
54.8
30.7
38.8
22.2
38.5
31.5
69.0
38.6
55.4
30.5
38.3
21.6
35.7
27.8
63.8
41.2
52.8
26.3
34.9
18.3
35.2
27.8
64.2
41.8
53.4
26.2 34.4
17.5
B3LYP/6-311+G**B3LYP/apdzMP2/6-311+G**MP2/apdzCCSD(T)/6-311+G(2df,2p) SP
normal form
TS1
tautomer_trans_out
tautomer_int
TS2 TS3
TS4
S0
tautomer_cis_out
tautomer_cis
4reaction pathways in triplet ground state at different methods
• It seems a structure that similar to the normal form at the MP2/6-311+G** and MP2/aug-cc-pVDZ levels.
78.3(17.0)
59.9(-1.3)
61.3(0.0)
77.0(15.8)
71.8(10.5) 78.7(0.0) 77.3(-1.4)
107.1(28.4)
77.3(-1.4) 78.8(0.1)
MP2/apdzMP2/aptz B3LYP/6-311+G** B3LYP/6-311+G** S0 geom. SPB3LYP/apdzMP2/6-311+G** CCSD(T)/6-311+G(2df,2p)//B3LYP
normal form(?) TS1 tautomer_trans_in
TS2
tautomer_trans_out
tautomer_cis
T1
cis_TS
trans_out_TS
Em.TD-B3LYP//B3LYP = 1002 nmB3LYP = 797 nm
Em.TD-B3LYP//B3LYP = 1648 nmB3LYP = 995 nm
Em.TD-B3LYP//B3LYP = 1628 nmB3LYP = 1040 nm
without parentheses : relative to singlet state normal form
unit: kcal/mol
5potential energy surface scan of tautomer R1 bond from 0.8 Å to 1.35Å in the triplet ground state
0.80 0.85 0.90 0.95 1.00 1.05 1.10 1.15 1.20 1.25 1.30 1.35 0
5
10
15
20
25
30
11.6
0.0
7.6 9.2
11.4
0.0
6.9
10.2
MP2/6-311+G**
B3LYP/6-311+G**
CCSD(T)/6-311+G(2df,2p)//B3LYP
CCSD(T)/6-311+G(2df,2p)//MP2
Relative energy (kcal/m
ol)
R1
(Å)R2 1.13 1.16 1.19 1.23 1.27 1.36 1.52 1.68 1.79 1.88 1.95 2.01 R2 1.19 1.16 1.22 1.30 1.40 1.52 1.64 1.74 1.83 1.90 1.96 2.01
• From the CCSD(T)/6-311+G(2df,2p) calculations, the normal form is 10 kcal/mol higher than tautomer_trans form in the triplet ground state, and the B3LYP functional gives the energies very close to the CCSD(T) values.
6
normal formTS1
tautomer_trans_in TS2 tautomer_int
TS3 tautomer_cis
singlet excited state reaction pathways
S1 geom. at CIS/6-311+G**
70.8(0.0) 73.3(2.5) 64.3(-6.5)
100.3(-16.1)
116.4(0.0) 112.2(-4.2)
97.6(-18.7)
77.0(0.0)(pipi*) 77.1(0.1) 75.7(-1.3)
96.5(0.0) 90.6(-5.9)
87.3(-9.2)
94.0(-2.5)
71.3(-25.2)
96.3(-0.2)
88.4(-8.1)
109.1(-15.7)(npi*)
*124.9(0.0)(pipi*)
119.2(-5.7)
111.6(-13.3)
119.1(-5.8)
106.4(-18.4)
121.7(-3.2)
110.9(-14.0)
CIS/6-311+G**TD-B3LYP/6-311+G** SPTD-B3LYP/6-311+G**CASSCF/6-311+G** SPCASPT2/6-311+G** SP
normal form
S1 or S2
TS1
tautomer_trans_in
TS2
tautomer_int
TS3
tautomer_cis
(CIS geom.)
(TD-B3LYP geom)
* using the nπ* geom
unit: kcal/mol
7singlet excited state reaction pathways
81.0(0.0) 79.1(-1.8) 72.3(-8.6)
87.2(6.2)
98.6(17.6)
87.9(7.0) 71.6(-9.4)
*96.5(0.0) 90.6(-5.9) 87.3(-9.2)
94.0(-2.5)
71.3(-25.2)
96.3(-0.2)
88.4(-8.1)
109.1(0.0)
133.7(24.6)
125.4(16.2)
156.2(47.1)
179.1(70.0)
156.3(47.2)
127.4(18.2) *124.9(0.0)
119.2(-5.7)
111.6(-13.3)
119.1(-5.8)
106.4(-18.4)
121.7(-3.2)
110.9(-14.0)
CIS/6-311+G** SP pipi* CIS/6-311+G** SP npi*TD-B3LYP/6-311+G** SP* pipi*TD-B3LYP/6-311+G** SP npi*
normal form
TS1
tautomer_trans_in
TS2
tautomer_int
TS3 tautomer_cis
8singlet excited state reaction pathways
86.1(0.0) 88.3(2.3) 83.5(-2.6)
99.8(13.8)
109.7(23.6)
99.8(13.8)
79.7(-6.3) 84.6(0.0) 84.1(-0.4) 81.3(-3.3)
87.3(2.7)
74.8(-9.8)
91.7(7.2) 84.8(0.2)
EOM-CCSD/6-311+G** SP pipi* EOM-CCSD/6-311+G** SP npi*
1.TD-B3LYP pipi* geom for normal, TS1, tautomer_trans_in, tautomer_cis2.CIS pipi* geom for TS2, tautomer_int, TS3
normal form TS1
tautomer_trans_in
TS2tautomer_int
TS3
tautomer_cis
1.TD-B3LYP pipi* geom for normal, TS1, tautomer_trans_in, tautomer_cis2.CIS pipi* geom for TS2, tautomer_int, TS3
9singlet excited state reaction pathways
76.0(0.0) 79.1(3.1)
61.0(-15.1)
86.6(10.6) 84.5(8.5)
76.0(0.0)
61.4(-14.7)
73.1(0.0)
74.6(1.5)
65.6(-7.4) 69.7(-3.4) 67.9(-5.1)
74.1(1.1) 72.0(-1.1)
110.1(0.0)
122.2(12.1)
95.0(-15.2)
109.3(-0.8)
93.4(-16.7)
78.1(-32.1) 77.6(-32.6)
116.4(0.0)
112.2(-4.2)
97.6(-18.7)
90.5(-25.9)
86.7(-29.7) 89.9(-26.5)
100.3(-16.1)
CAS/6-311+G** SP pipi* CAS/6-311+G** SP npi*CASPT2/6-311+G** SP* pipi*CASPT2/6-311+G** SP npi*
normal form
TS1
tautomer_trans_in
TS2
tautomer_intTS3
tautomer_cis
1.TD-B3LYP pipi* geom for normal, TS1, tautomer_trans_in, tautomer_cis2.CIS pipi* geom for TS2, tautomer_int, TS3
10singlet excited state reaction pathways
52.6(-5.2)[-3.9]
57.1(-4.7)
70.9(0.0)[1.8]
57.8(0.0)[0.0]
64.6(6.8)[5.3]
51.1(-6.7)[-5.6]
70.8(0.0)[0.0]
73.3(2.5)[1.3]
64.3(-6.5)[-5.7]
77.3(0.3)
61.8(0.0)
61.9(0.1)
55.8(-5.9)
TD-B3LYP/6-311+G** pipi*TD-B3LYP/6-311+G** npi*CASPT2(7,8)/6-311+G** SP pipi*CASPT2(7,8)/6-311+G** SP npi*normal form
tautomer_trans_in tautomer_cisTS
11singlet excited state summary
normal form npi* state energies relative to the pipi* state (kcal/mol)
CIS -15.7TD-B3LYP SP -15.5
TD-B3LYP -21.9CASSCF SP -6.2CASPT2 SP 3.7
52.6(-5.2)[-3.9] 57.1(-4.7)
17.5
0.0
35.2 27.8
70.9(0.1)[1.8]
57.8(0.0)[0.0] 64.6(6.8)[5.3]
51.1(-6.7)[-5.6]
70.8(0.0)[0.0] 73.3(2.5)[1.3]
64.3(-6.5)[-5.7]
100.3(-16.1)
116.4(0.0) 112.2(-4.2)
97.6(-18.7)
77.3(0.3)
61.8(0.0)
61.9(0.1) 55.8(-5.9)
CIS/6-311+G**TD-B3LYP/6-311+G** SPTD-B3LYP/6-311+G** pipi*TD-B3LYP/6-311+G** npi*CASSCF(8,7)/6-311+G** SPCASPT2(8,7)/6-311+G** SP pipi*CASPT2(8,7)/6-311+G** SP npi*B3LYP/6-311+G** S0
normal form
tautomer_trans_in tautomer_cisTS
tautomer_trans_out
S0
S1 or S2
Abs.CASPT2 = 344 nmExpt. = 342 nm
Em.CASPT2 = 501 nmExpt. = 508 nm
Em.CASPT2 = 533 nmExpt. = 508 nm
without parentheses : relative to singlet state normal formin the brackets : including zero-point energy
12Absorption spectrum
λcalc. (nm) normal form (CYH)
normal form (MeOH)
normal form (H2O)
normal form (gas phase)
TD-B3LYP/6-311+G** SP 306.6 306.17 306.2 301.9 TD-B3LYP/6-31+G** SP 303.3 TD-B3LYP/aug-cc-pVDZ SP 307.0 TD-M06-2X/6-311+G** SP 273.2EOM-CCSD/6-311+G** SP 280.3CASSCF/6-311+G** SP 203.0CASPT2/6-311+G** SP, shift=0.1 344.2
13Emission spectrum
λcalc. (nm) tautomer_trans_in tautomer_cisCIS/6-311+G** 321.3 344.5 TD-B3LYP/6-311+G** SP 391.0 426.1 TD-B3LYP/6-311+G** 417.3 473.9 CASSCF/6-311+G** SP 372.9 421.2CASPT2/6-311+G** SP 500.6 533.1
14Normal form structures
unit : angstrom degree S0 R1 R2 A1 A2 A3 A4
B3LYP/6-31+G** 0.989 1.764 107.7 122.5 120.5 123.3 CsB3LYP/6-311+G** 0.984 1.781 107.8 122.7 120.5 123.4 Cs
B3LYP/apdz 0.989 1.750 107.2 122.3 120.3 123.3 CsMP2/6-311+G** 0.979 1.794 106.6 123.0 120.6 123.4 Cs
MP2/apdz 0.987 1.781 106.5 122.7 120.6 123.3 CsMP2/aptz 0.985 1.757 106.4 122.5 120.6 123.4 Cs
CASPT2(8,7)/6-311+G** 0.978 1.800 106.8 122.9 120.8 123.4 CsT1
MP2/6-311+G** 1.259 1.162 102.7 117.1 117.6 120.6 CsMP2/apdz 1.264 1.177 102.7 117.2 117.9 120.5 CsMP2/aptz 1.270 1.162 102.7 117.3 118.0 120.6 Cs
S1 or S2 CIS/6-311+G** 0.942 2.032 113.2 124.6 121.7 125.5 C1-npi*CIS/6-311+G** 0.973 1.696 109.7 119.2 119.5 123.0 Cs-pipi*
TD-B3LYP/6-311+G** 1.085 1.412 104.7 118.9 119.1 120.2 C1-pipi*TD-B3LYP/6-311+G** 1.087 1.411 104.9 118.0 118.5 120.7 Cs-pipi*
15tautomer_trans_in structures
T1 R1 R2 A1 A2 A3 A4 B3LYP/6-311+G** 1.763 0.988 107.3 120.0 120.4 124.2 Cs
B3LYP/apdz 1.733 0.993 106.7 120.0 120.3 123.6 CsMP2/6-311+G** 1.692 0.994 105.0 119.7 120.7 123.4 Cs
MP2/apdz 1.650 1.009 104.6 119.5 120.5 122.8 CsMP2/aptz 1.606 1.012 104.3 119.4 120.1 122.5 Cs
S1 or S2 CIS/6-311+G** 1.769 0.967 109.0 118.5 120.1 125.1 C1
TD-B3LYP/6-311+G** 1.551 1.038 104.7 118.9 119.1 122.5 CsCASPT2(8,7)/6-311+G** 1.490 1.047 102.6 117.6 119.1 121.7 Cs
16tautomer_trans_out structures
unit :angstrom degree S0 R1 A1 A2 A3 A4
B3LYP/6-311+G** 0.964 123.9 123.7 124.5 110.1 CsB3LYP/apdz 0.966 123.7 123.7 124.2 109.9 Cs
MP2/6-311+G** 0.964 123.8 123.3 124.1 108.6 CsMP2/apdz 0.970 123.6 123.2 123.7 108.7 Cs
T1 B3LYP/6-311+G** 0.963 122.1 123.9 123.3 109.4 Cs
B3LYP/apdz 0.966 121.9 124.0 123.1 109.3 CsMP2/6-311+G** 0.962 121.6 126.1 123.4 108.0 Cs
17tautomer_cis structures
unit : angstrom degree S0 R1 R2 A1 A2 A3
B3LYP/6-311+G** 0.982 2.082 106.0 122.0 114.7 CsB3LYP/apdz 0.984 2.080 105.7 121.9 114.7 Cs
MP2/6-311+G** 0.980 2.056 104.7 122.1 114.1 CsMP2/apdz 0.987 2.051 104.6 121.7 113.9 Cs
CASPT2(8,7)/6-311+G** 0.977 2.088 105.2 122.7 114.4 CsT1
B3LYP/6-311+G** 0.981 2.063 106.0 118.5 116.5 CsB3LYP/apdz 0.983 2.062 105.7 118.4 116.5 Cs
MP2/6-311+G** 0.976 2.076 105.2 120.4 115.5 CsS1 or S2
CIS/6-311+G** 0.954 2.175 109.2 120.6 117.8 CsTD-B3LYP/6-311+G** 0.990 2.020 105.7 118.1 116.1 Cs
CASPT2(8,7)/6-311+G** 0.999 1.929 104.0 117.1 114.8 Cs
N CO
NH2
OH
N CO
OCH3
OH
N CO
H
OH
3-hydroxypicolinamide 3-hydroxypicolinaldehyde3-hydroxypicolin-methylester
Chem. Phys. Lett. 1989, 161, 361
Predicted S1 configuration
pp* pp* np*
N
O
O
H
OP
OH
HO
O
Vitamin B6
Truncation
N
O
O
H
Parent molecule
An Isomer of
N
OH
O
3-hydroxypicolinaldehydein our study
Significance of the above results and discussion
N
O
O
H
N
O
O
HNH2
N
O
O
HOCH3
np*
Predicted S1 Conf iguration
pp* pp*Lack of ESIPT ESIPT ESIPT
3-hydroxypicolinaldehyde(3HPAL)3-hydroxypicolinamide(3HPAM)
2013/02/26
N
O
O
N
H
HH
N
O
O
H
H
最新 2013/2/26 所算的檔
223-hydroxypicolinaldehyde(3HPAL)
?
23
Absorption Spectrumnormal form λ (nm) oscillator strength
CIS/6-311+G** SP 251.0 0.000 S1-npi* 236.2 0.273 S2-pipi*TD-B3LYP/6-311+G** SP 347.2 0.000 S1-npi* 301.9 0.123 S2-pipi*
EOM-CCSD/6-311+G** SP 306.5 0.000 S1-npi* 280.3 0.139 S2-pipi*CAS(7,8)/6-31+G** SP 241.8 0.000 S1-npi* 203.0 0.534 S2-pipi*
CASPT2(7,8)/6-31+G** SP 352.6 S1-npi* 344.2 S2-pipi*Expt. 315.0
24
Emission Spectrumnormal form λ (nm)
CIS/6-311+G** 228.9 S2-pipi*TD-B3LYP/6-311+G** SP 296.3 S2-pipi*
TD-B3LYP/6-311+G** 371.1 S2-pipi*CAS(7,8)/6-311+G** SP 245.6 S2-pipi*
CASPT2(7,8)/6-311+G** 403.9 S2-pipi*tautomer_trans λ (nm)
CIS/6-311+G** 321.3 S1-pipi*TD-B3LYP/6-311+G** SP 391.0 S2-pipi*
TD-B3LYP/6-311+G** 417.3 S2-pipi*CAS(7,8)/6-311+G** SP 372.9 S2-pipi*
CASPT2(7,8)/6-311+G** SP 500.6 S2-pipi*tautomer_cis λ (nm)
CIS/6-311+G** 344.5 S1-pipi*TD-B3LYP/6-311+G** SP 426.1 S2-pipi*
TD-B3LYP/6-311+G** 473.9 S2-pipi*CAS(7,8)/6-311+G** SP 421.2 S2-pipi*
CASPT2(7,8)/6-311+G** SP 533.1 S2-pipi*Expt. 360.0
25
26Singlet excited states at TD-B3LYP/6-311+G**
83.8 75.5(0.0) 75.6(0.1)
69.5(-5.9)
94.7 87.8(0.0) 87.9(0.1)
86.5(-1.3)
S2(pipi*)S1(npi*)S0
λAbs.TD-B3LYP = 302 nmExpt. = 315 nm
λEm.TD-B3LYP = 417 nm
λEm.TD-B3LYP = 474 nm
λEm.Expt. = 360 nm
N
N* TS T_trans* T_cis*
unit: kcal/mol
λEm.TD-B3LYP = 371 nm
f=0.1023(S2)f=0.0001(S1)
f=0.1144(S2)f=0.0002(S1)
f=0.0933(S2)f=0.0002(S1)
27Singlet excited states at CASPT2(7,8)/6-311+G**
82.9 72.8(0.0)
79.6(6.8)66.1(-6.7)
86.3 79.5(0.0) 82.0(2.5)
72.9(-6.5)
S2(pipi*)S1(npi*)S0
λAbs.CASPT2 = 344 nmExpt. = 315 nm
λEm.CASPT2 = 501 nm
λEm.CASPT2 = 533 nm
λEm.Expt. = 360 nm
N
N* TST_trans*
T_cis*
unit: kcal/mol
λEm.CASPT2 = 404 nm
283-hydroxypicolinamide(3HPAM)
29
Emission Spectrumtautomer λ (nm)
CIS/6-311+G** 309.5 S1-pipi*TD-B3LYP/6-311+G** SP 383.7 S2-pipi*
EOM-CCSD/6-311+G** SP 378.4 S1-pipi*CAS(12,16)/6-311+G** SP 315.3 S1-pipi*
CASPT2(12,16)/6-311+G** SP 457.9 S1-pipi*Expt. 430.0
Absorption Spectrum λ (nm) oscillator strength
CIS/6-311+G** SP 228.5 0.259 S1-pipi* 209.4 0.004 S2-npi*TD-B3LYP/6-311+G** SP 289.6 0.001 S1-npi* 283.4 0.145 S2-pipi*
EOM-CCSD/6-311+G** SP 270.0 0.133 S1-pipi* 252.5 0.001 S2-npi*EOM-CCSD/6-311+G(2df,2pd) SP 271.7 0.135 S1-pipi* 254.4 0.001 S2-npi*
CAS/6-311+G** SP 229.4 0.275 S1-pipi* 215.7 0.000 S2-npi*
CASPT2/6-311+G** SP 307.9 S1-pipi* 270.6 S2-npi*Expt. 305.0
30
(a) absorption spectrum of 3HP (1.5x10-5 M) in MCH; (b) absorption spectrum of 3MP (1.9x10-5 M) in MCH; (c) emission spectrum of 3HP in MCH at room temperature (λex = 300 nm);(c' ) excitation spectrum of 3HP in MCH monitored at 430 nm; (d) emission spectrum of 3HP at 77 Kin MCH glass (λex = 300 nm).
31Singlet excited states at TD-B3LYP/6-311+G**
98.7
101.1(0.0)
99.5(-1.6)
89.9(-11.2)
100.9
100.0(0.0)
97.3(-2.7)
93.8(-6.2)
S2(pipi*)S1(npi*)S0
λAbs.TD-B3LYP = 283 nmExpt. = 305 nm
λEm.TD-B3LYP = 384 nmExpt. = 430 nm
N
N* TST*
unit: kcal/mol
f=0.1836(S2)f=0.0003(S1)
32Singlet excited states at CASPT2(12,16)/6-311+G**
105.7 106.9(0.0) 102.3(-4.6)
89.1(-17.8)92.9 90.6(0.0)
86.1(-4.5) 85.2(-5.4)
S2(pipi*)S1(npi*)S0
λAbs.CASPT2 = 308 nmExpt. = 305 nm
λEm.CASPT2 = 458 nmExpt. = 430 nm
N
N* TST*
unit: kcal/mol
33Singlet excited states at EOM-CCSD/6-311+G**
113.2
116.2(0.0) 115.5(-0.6)
108.0(-8.1)
105.9 103.9(0.0)
101.8(-2.1)98.8(-5.2)
S2(pipi*)S1(npi*)S0
λAbs.EOM-CCSD = 270 nmExpt. = 305 nm
λEm.EOM-CCSD = 378 nmExpt. = 430 nm
N
N* TST*
unit: kcal/mol
f=0.0005(S2)f=0.2545(S1)