1. Kirin 2012/11/30

2. reaction pathways at different methods 2

3. reaction pathways in singlet ground state at different methods There are no tautomer_trans_in forms in the singlet ground state at differenet methods. 3

4. reaction 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. 4

5. potential energy surface scan of tautomer R1 bond from 0.8 Å to 1.35Å in the triplet ground state 5 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 form TS1 tautomer_trans_in TS2 tautomer_int TS3 tautomer_cis singlet excited state reaction pathways S1 geom. at CIS/6-311+G** 6

7. singlet excited state reaction pathways 7

8. 8

9. 9

10. 10

11. singlet excited state summary 11 normal form npi* state energies relative to the pipi* state (kcal/mol) CIS  15.7 TD-B3LYP SP  15.5 TD-B3LYP  21.9 CASSCF SP  6.2 CASPT2 SP3.7

12. Absorption spectrum λcalc. (nm) normal form (CYH) normal form (MeOH) normal form (H 2 O) normal form (gas phase) TD-B3LYP/6-311+G** SP306.6306.17306.2301.9 TD-B3LYP/6-31+G** SP303.3 TD-B3LYP/aug-cc-pVDZ SP307.0 TD-M06-2X/6-311+G** SP273.2 EOM-CCSD/6-311+G** SP280.3 CASSCF/6-311+G** SP203.0 CASPT2/6-311+G** SP, shift=0.1344.2 12

13. Emission spectrum λcalc. (nm)tautomer_trans_intautomer_cis CIS/6-311+G**321.3344.5 TD-B3LYP/6-311+G** SP391.0426.1 TD-B3LYP/6-311+G**417.3473.9 CASSCF/6-311+G** SP372.9421.2 CASPT2/6-311+G** SP500.6533.1 13

14. Normal form structures 14 unit :angstromdegree S0R1R2A1A2A3A4 B3LYP/6-31+G**0.9891.764107.7122.5120.5123.3Cs B3LYP/6-311+G**0.9841.781107.8122.7120.5123.4Cs B3LYP/apdz0.9891.750107.2122.3120.3123.3Cs MP2/6-311+G**0.9791.794106.6123.0120.6123.4Cs MP2/apdz0.9871.781106.5122.7120.6123.3Cs MP2/aptz0.9851.757106.4122.5120.6123.4Cs CASPT2(8,7)/6-311+G**0.9781.800106.8122.9120.8123.4Cs T1 MP2/6-311+G**1.2591.162102.7117.1117.6120.6Cs MP2/apdz1.2641.177102.7117.2117.9120.5Cs MP2/aptz1.2701.162102.7117.3118.0120.6Cs S1 or S2 CIS/6-311+G**0.9422.032113.2124.6121.7125.5C1-npi* CIS/6-311+G**0.9731.696109.7119.2119.5123.0Cs-pipi* TD-B3LYP/6-311+G**1.0851.412104.7118.9119.1120.2C1-pipi* TD-B3LYP/6-311+G**1.0871.411104.9118.0118.5120.7Cs-pipi*

15. tautomer_trans_in structures 15 T1R1R2A1A2A3A4 B3LYP/6-311+G**1.7630.988107.3120.0120.4124.2Cs B3LYP/apdz1.7330.993106.7120.0120.3123.6Cs MP2/6-311+G**1.6920.994105.0119.7120.7123.4Cs MP2/apdz1.6501.009104.6119.5120.5122.8Cs MP2/aptz1.6061.012104.3119.4120.1122.5Cs S1 or S2 CIS/6-311+G**1.7690.967109.0118.5120.1125.1C1 TD-B3LYP/6-311+G**1.5511.038104.7118.9119.1122.5Cs CASPT2(8,7)/6-311+G**1.4901.047102.6117.6119.1121.7Cs

16. tautomer_trans_out structures 16 unit :angstromdegree S0R1A1A2A3A4 B3LYP/6-311+G**0.964123.9123.7124.5110.1Cs B3LYP/apdz0.966123.7 124.2109.9Cs MP2/6-311+G**0.964123.8123.3124.1108.6Cs MP2/apdz0.970123.6123.2123.7108.7Cs T1 B3LYP/6-311+G**0.963122.1123.9123.3109.4Cs B3LYP/apdz0.966121.9124.0123.1109.3Cs MP2/6-311+G**0.962121.6126.1123.4108.0Cs

17. tautomer_cis structures 17 unit :angstromdegree S0R1R2A1A2A3 B3LYP/6-311+G**0.9822.082106.0122.0114.7Cs B3LYP/apdz0.9842.080105.7121.9114.7Cs MP2/6-311+G**0.9802.056104.7122.1114.1Cs MP2/apdz0.9872.051104.6121.7113.9Cs CASPT2(8,7)/6-311+G**0.9772.088105.2122.7114.4Cs T1 B3LYP/6-311+G**0.9812.063106.0118.5116.5Cs B3LYP/apdz0.9832.062105.7118.4116.5Cs MP2/6-311+G**0.9762.076105.2120.4115.5Cs S1 or S2 CIS/6-311+G**0.9542.175109.2120.6117.8Cs TD-B3LYP/6-311+G**0.9902.020105.7118.1116.1Cs CASPT2(8,7)/6-311+G**0.9991.929104.0117.1114.8Cs

18. Chem. Phys. Lett. 1989, 161, 361 Predicted S 1 configuration  * n*n*

19. Significance of the above results and discussion

21. 3-hydroxypicolinaldehyde(3HPAL) 3-hydroxypicolinamide(3HPAM) 2013/02/26 最新 2013/2/26 所算的檔

22. 3-hydroxypicolinaldehyde(3HPAL) 22 ?

23. 23 Absorption Spectrum normal formλ (nm)oscillator strength CIS/6-311+G** SP251.00.000S1-npi* 236.20.273S2-pipi* TD-B3LYP/6-311+G** SP347.20.000S1-npi* 301.90.123S2-pipi* EOM-CCSD/6-311+G** SP306.50.000S1-npi* 280.30.139S2-pipi* CAS(7,8)/6-31+G** SP241.80.000S1-npi* 203.00.534S2-pipi* CASPT2(7,8)/6-31+G** SP352.6S1-npi* 344.2 S2-pipi* Expt.315.0

24. 24 Emission Spectrum normal formλ (nm) CIS/6-311+G**228.9S2-pipi* TD-B3LYP/6-311+G** SP296.3S2-pipi* TD-B3LYP/6-311+G**371.1S2-pipi* CAS(7,8)/6-311+G** SP245.6S2-pipi* CASPT2(7,8)/6-311+G**403.9S2-pipi* tautomer_transλ (nm) CIS/6-311+G**321.3S1-pipi* TD-B3LYP/6-311+G** SP391.0S2-pipi* TD-B3LYP/6-311+G**417.3S2-pipi* CAS(7,8)/6-311+G** SP372.9S2-pipi* CASPT2(7,8)/6-311+G** SP500.6S2-pipi* tautomer_cisλ (nm) CIS/6-311+G**344.5S1-pipi* TD-B3LYP/6-311+G** SP426.1S2-pipi* TD-B3LYP/6-311+G**473.9S2-pipi* CAS(7,8)/6-311+G** SP421.2S2-pipi* CASPT2(7,8)/6-311+G** SP533.1S2-pipi* Expt.360.0

25. 25

26. Singlet excited states at TD-B3LYP/6-311+G** 26

27. Singlet excited states at CASPT2(7,8)/6-311+G** 27

28. 3-hydroxypicolinamide(3HPAM) 28

29. 29 Emission Spectrum tautomerλ (nm) CIS/6-311+G**309.5S1-pipi* TD-B3LYP/6-311+G** SP383.7S2-pipi* EOM-CCSD/6-311+G** SP378.4S1-pipi* CAS(12,16)/6-311+G** SP315.3S1-pipi* CASPT2(12,16)/6-311+G** SP457.9S1-pipi* Expt.430.0 Absorption Spectrum λ (nm)oscillator strength CIS/6-311+G** SP228.50.259S1-pipi* 209.40.004S2-npi* TD-B3LYP/6-311+G** SP289.60.001S1-npi* 283.40.145S2-pipi* EOM-CCSD/6-311+G** SP270.00.133S1-pipi* 252.50.001S2-npi* EOM-CCSD/6-311+G(2df,2pd) SP271.70.135S1-pipi* 254.40.001S2-npi* CAS/6-311+G** SP229.40.275S1-pipi* 215.70.000S2-npi* CASPT2/6-311+G** SP307.9S1-pipi* 270.6 S2-npi* Expt.305.0

30. 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).

31. Singlet excited states at TD-B3LYP/6-311+G** 31

32. Singlet excited states at CASPT2(12,16)/6-311+G** 32

33. Singlet excited states at EOM-CCSD/6-311+G** 33