The study of two previous papers in REMPI sepectra Jingming Long 2010.03.29.

The study of two previous papers in REMPI sepectra

Jingming Long

2010.03.29

Agust Kavran, Huasheng Wang, Ashildur Logadottir. Resonance enhanced multiphoton ionization of hydrogen halides: rotational structure and anomalies in Rydberg and ion-pair states of HCL and HBr[J]. J.Chemical Physics. 2000,112(24):10811-10820.

Agust Kavran, Huasheng Wang, Kristian Matthiasson, et al. Two-dimensional (2+n) resonance enhanced multiphoton ionization of HCl: photorupture channels via the F 1∆2 Rydberg state and ab initio spectra[J]. J.Chemical Physics. 2008,129:164313.

Support

Conform

The First Paper The Second Paper

Purpose Derive energy of rotational levels in the F,E,V states for HCl(H35Cl,H37Cl) and HBr(H79Br ,H81Br).

Quantify the contribution of Rydberg and valence intermediate states to the photoionization product formation.

Method• (2+1)REMPI-TOF• Perturbation theory• Analysis of rotational line shifts

and Intensity alteration

1. 2D(2+n)REMPI-TOF

2. Time dependent-density functional theory (TD-DFT),

3. Equation-of-motion coupled cluster (EOM-CC)

4. Analysis of Relative ion-signal intensity alteration, power dependent

Results

a) The first time to find near resonance interaction between the F and V states for HCl, HBr.

b) Spectroscopy parameters (table1) are similar with others.

c) off-resonance interaction between E and V states

d) A model calculation for states interaction is made well for HCl.

a) Interpreted the different photoionization channels via Rydberg states and ion-pair states successfully.

b) Evaluated state interaction strength.

c) Obtained vibrational and rotational spectroscopic parameters.

The First Paper

Repulsion

Compression

8,7),14()1( ''' JVF

6,5),18()2( ''' JVF

7),11,10()0( ''' JVE

6,5),7()1( ''' JmVF

a) HCl

b) HBr

Resonance Interaction：

2/1202

01

2

1202

01 ])(4[

4

1)(

2

1EEWEEEi

02E

2E

01E

1E

From experiment data From theory calculation

Unperturbed

Perturbed

W12

The Second Paper

What do we mainly do?

Find new states.Derive the energy of vibrational and rotational levelsSimulate relevant spectra.Compare experiment data with theory result and obtain spectroscopic parameters. Interpret photodissociation and photoionization mechanism.

What can we use?

TECHNOLOGY: REMPI-TOF

ANALYSIS METHOD: Power Dependence Theory Simulation 2D(m+n), m=2,3. n=1,2..

Thank you！