PULSED-FIELD IONIZATION ELECTRON SPECTROSCOPY AND AB INITIO CALCULATIONS

OFMETAL (Li, Ca, Sc) COMPLEXES OF PYRIDINE AND

PYRIDAZINE

Sergiy Krasnokutski and Dong-Sheng Yang

University of Kentucky, Lexington, KY 40506, USA

$ National Science Foundation $

1. J. Miyawaki and K.-i. Sugawara, Chem. Phys. Lett. 386, 196 (2004).

4.43 Debye2.37 Debye

Background

2. X. Wang, B. R. Sohnlein, S. G. Li, J. F. Fuller, and D. S. Yang, Canadian Journal of Chemistry-Revue Canadienne De Chimie 85 (10), 714 (2007).

4. W. Y. Guo, H. C. Liu, and S. H. Yang, Int. J. Mass. Spectrom 226 (2), 291 (2003).

CuMg

M. T. Rodgers, J. R. Stanley, and R. Amunugama, J. Am. Chem. Soc. 122 (44), 10969 (2000).

4.43 Debye2.37 Debye

Mg+, Al+, Sc+, Ti+, V+, Cr+, Mn+, Fe+,Co+, Ni+, Cu+, and Zn+

Background

R. Amunugama and M. T. Rodgers, Int. J. Mass. Spectrom 196, 439 (2000).

4.43 Debye2.37 Debye

Background

HV

M CP

TP 400L/s

TP 400L/sDP 2300L/s

Extraction Cans

Tim e of Flight Tube

M etal

G ateValve

Sk immer

H e 30 p si

P u lsed Va lve

53 2 n m

M eta l R od

ZEKE experimental setup

IE=32460 cm-1

Wavenumber (cm-1)

Li-pyridine

-200 0 200 400 600 800 1000

216

Wavenumber (cm-1)

Experiment

216144

Ca-pyridine experimental / B3LYP simulation

IE= 39064 cm-1

HOMOs of Li-pyridine and Ca-pyridine

Li-Pyridine Ca-Pyridine

0 200 400 600 800 1000 1200 1400 1600

456534

Exp.

Wavenumber (cm-1)

374

50

Sc-pyridine experimental / B3LYP simulation

IE= 42654 cm-1

1A'2A'

1A'2A"

3A"4A"

1A12B1

E (cm-1)

2266

0

2948

5105

0 500 1000 1500 2000 2500 3000

R

ela

tive

In

ten

sity

Wavenumber (cm-1)

Li-pyridazine experimental / B3LYP simulation

IE= 37870 cm-1

-200 0 200 400 600 800 1000 1200 1400 1600

Wavenumber (cm-1)

Observed vibrational modes of Li-pyridazine

HOMOs of Li-pyridine and Li-pyridazine

Li-pyridine Li-pyridazine

Li-pyridazineLUMO

Ca-pyridazine experimental / MP2 simulation -1

58

052 24

0

400

452

638

680

798

850

1038

1086

1196

1246

1480 15

9416

48 2052 24

06

-200 0 200 400 600 800 1000 1200 1400 1600 1800 2000

241

398

Wavenumbers (cm-1)

398398

Ar

He

398

IE= 41928 cm-1

Li-pyridine Ca-pyridine Sc-pyridine Li-pyridazine Ca-pyridazine

Type of the bond ?

dissociation energy (cm-1)Experiment*

4187 - 9288 13977 -

dissociation energy (cm-1)calculation

4215 2368 8679 13206 ???

Ionization energy (cm-1)experiment

32460 39064 42816 37870 41928

Ionization energy (cm-1)calculation

33506 38602 42654 38921 4177945035

Ionization and dissociation energies of the complexes

* where from collision induced dissociation experiment )()()()(D 00 LMIEMIELMDLM )(0 LMD