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)