Theoretical Prediction of the Near-edge X-ray Absorption Fine

Structure of Peptides
Cheng-Cheng Tsai( ) , Wei-Ping Hu*( )
Department of Chemistry and Biochemistry, National Chung Cheng University, Chiayi, Taiwan
( )

1s * core excitation carboxyl group * 1s

Rydberg orbitals 1s core excitation energy 1s
core excitation energy (1) core orbital (2)
virtual orbital TDDFT bound state
TDDFT Near edge X-ray absorption fine structure

1920 X-ray (NEXAFS(Near-edge X-ray Absorption

Fine Structure) carbonate C: 1s * aldehyde C: 1s *
4 eV X-ray Auger decay
bound state
bound state NEXAFS NEXAFS transition potential
NEXAFS 1.5 ~ 2 eV Equation-of-Motion Coupled-Cluster (EOM-CCSD)
NEXAFS EOM-CCSD Density Functional Theory Time
Dependent Density Functional Theory (TDDFT) TDDFT NEXAFS 1
functional NEXAFS carbonyl group
benzene NEXAFS
TDDFT Glycine tyrosine peptide NEXAFS

B3LYP/6-311+G(d,p)
Gaussian 09 D01 NEXAFS Tamm
Dancoff2 Time Dependent Density Functional Theory
(TDDFT) functional LB94
Pople 6-31+G(d,p)
Q-CHEM 4.1

Figure 1. Glycyltyrosine

Figure 2. Tyrosylglycine

1.

Figure 1 2 peptide tyrosylglycine

glycyltyrosine 0.8 kcal/mol Figures 3 carbon K-

edge NEXAFS Figure 4 *

peptide 285 eV
( A) 285ev
1s *
B 1s
* C D carbonyl group
1s carbonyl group * D
1s Rydberg orbital
A B 285 287 eV phenol carbon
K-edge NEXAFS transition *
1s
1s 2eV C D 288 eV
N-formmethylamide N-methylacetamide carbon Kedge NEXAFS carbonyl group 1s 288
eV
2.

peptide
NEXAFS
(
) (
) carbonyl group
285 287 288 eV *
( Figure 2) * *
carbonyl group LUMO carbonyl group *
LUMO+1 LUMO+3 *
1s * carbonyl group
1s carbonyl group *
NEXAFS

NEXAFS
carbon K-edge NEXAFS
peptide carbon K-egde
285 287 288 eV carbon K-edge
1s - (
) (
) carbonyl group LUMO
* - * carbonyl group
* transition
Rydberg states
amide phenol peptide
NEXAFS

Figure 3. Glycine Tyrosine peptide

peptide

Figure 4. * carbonyl group * *

1. Nicholas, A. B.; Frans A, A. Phys. Chem. Chem. Phys. 2010, 12, 12024.
2.Stener, M.; Fronzoni, G.; De Simone, M. Chem. Phys. Lett, 2003, 373, 115.
3.So, H.; Martin, H. G. Chem. Phys. Lett. 1999, 314, 291.
4.Boese, J.; Osanna, A.; Jacobsen, C.; Kirz, J. J. Electron. Spectrosc. Relat. Phenom. 1997, 85, 9.