Kirin 2012/11/30

reaction pathways at different methods 2

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

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

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.

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

singlet excited state reaction pathways 7

8

9

10

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

Absorption spectrum λcalc. (nm) normal form (CYH) normal form (MeOH) normal form (H 2 O) normal form (gas phase) TD-B3LYP/6-311+G** SP 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=

Emission spectrum λcalc. (nm)tautomer_trans_intautomer_cis CIS/6-311+G** TD-B3LYP/6-311+G** SP TD-B3LYP/6-311+G** CASSCF/6-311+G** SP CASPT2/6-311+G** SP

Normal form structures 14 unit :angstromdegree S0R1R2A1A2A3A4 B3LYP/6-31+G** Cs B3LYP/6-311+G** Cs B3LYP/apdz Cs MP2/6-311+G** Cs MP2/apdz Cs MP2/aptz Cs CASPT2(8,7)/6-311+G** Cs T1 MP2/6-311+G** Cs MP2/apdz Cs MP2/aptz Cs S1 or S2 CIS/6-311+G** C1-npi* CIS/6-311+G** Cs-pipi* TD-B3LYP/6-311+G** C1-pipi* TD-B3LYP/6-311+G** Cs-pipi*

tautomer_trans_in structures 15 T1R1R2A1A2A3A4 B3LYP/6-311+G** Cs B3LYP/apdz Cs MP2/6-311+G** Cs MP2/apdz Cs MP2/aptz Cs S1 or S2 CIS/6-311+G** C1 TD-B3LYP/6-311+G** Cs CASPT2(8,7)/6-311+G** Cs

tautomer_trans_out structures 16 unit :angstromdegree S0R1A1A2A3A4 B3LYP/6-311+G** Cs B3LYP/apdz Cs MP2/6-311+G** Cs MP2/apdz Cs T1 B3LYP/6-311+G** Cs B3LYP/apdz Cs MP2/6-311+G** Cs

tautomer_cis structures 17 unit :angstromdegree S0R1R2A1A2A3 B3LYP/6-311+G** Cs B3LYP/apdz Cs MP2/6-311+G** Cs MP2/apdz Cs CASPT2(8,7)/6-311+G** Cs T1 B3LYP/6-311+G** Cs B3LYP/apdz Cs MP2/6-311+G** Cs S1 or S2 CIS/6-311+G** Cs TD-B3LYP/6-311+G** Cs CASPT2(8,7)/6-311+G** Cs

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

Significance of the above results and discussion

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

3-hydroxypicolinaldehyde(3HPAL) 22 ?

23 Absorption Spectrum normal formλ (nm)oscillator strength CIS/6-311+G** SP S1-npi* S2-pipi* TD-B3LYP/6-311+G** SP S1-npi* S2-pipi* EOM-CCSD/6-311+G** SP S1-npi* S2-pipi* CAS(7,8)/6-31+G** SP S1-npi* S2-pipi* CASPT2(7,8)/6-31+G** SP352.6S1-npi* S2-pipi* Expt.315.0

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

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

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

3-hydroxypicolinamide(3HPAM) 28

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 Absorption Spectrum λ (nm)oscillator strength CIS/6-311+G** SP S1-pipi* S2-npi* TD-B3LYP/6-311+G** SP S1-npi* S2-pipi* EOM-CCSD/6-311+G** SP S1-pipi* S2-npi* EOM-CCSD/6-311+G(2df,2pd) SP S1-pipi* S2-npi* CAS/6-311+G** SP S1-pipi* S2-npi* CASPT2/6-311+G** SP307.9S1-pipi* 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).

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

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

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