CHINESE JOURNAL OF PHYSICS VOL. 29, NO.

2 APRIL 1991

Study of Electronic Autoionization of NO Molecule

by Excited-State Photoelectron Spectroscopy

Katsumi Kimura
Institute for Molecular Science
Okazaki 444, Japan
(Revised manuscript received Jan. 20, 1991)

In the present paper, recent applications of a resonant multiphoton ionization photo-

electron technique to the study of autoionization of NO molecule are demonstrated in the
following three cases: (a) autoionization occurring by (2 + 1) resonant excitation via Rydberg A
state, (b) autoionization occurring by (2 + 1) resonant excitation via valence B state, and (c)
autoionization occurring by (2 t 1) resonant excitation via higher valence B’ state.

I. INTRODUCTION

During last several years, the laser photoelectron spectrosocopy of resonant multi-
photon ionization of molecules in the gas phase have provided various important informa-
tions about the photoionization of excited molecules by identifying their final ionic states
from photoelectron spectra. This situation has recently been reviewed by the autor.lV2
This technique has been applied to NO molecule by Achiba et a1.334 to study its super-
excited states associated with autoionization. Photoelectron spectra give us quantitative
information about the branching ratios of producing ionic states (various electronic and
vibrational states of ions). In order to study autoionization, the resulting photoelectron
spectrum should be distinguished from that of direct ionization.
Two processes in which direct ionization is expected to be forbidden in the one-
electron ionization approximation are schematically illustrated in Fig. 1, the shaded area
indicating such forbidden region. Process (a) in Fig. 1 shows that the direct ionization of
Av = 0 transition through the A v’ = 0 state of NO gives rise to the v’s 0 ground state ion.
Process (b) in Fig. 1 indicates that such direct ionization is essentially forbidden in the sense
of Franck-Condon selection rule, while process (b) Fig. 1 shows that direct ionization is
electronically forbidden in the sense of one-electron transition.
Selective excitation is especially advantageous for studying autoionization of
molecules.4 Two-color experiments are most desirable for this purpose. However, one-
color experiments are sometime useful to study autoionization, if accidental resonance

97

-_l___-_. ._
., . .,
 98 STUDY OF ELEaRONIC AUTOIONIZATION OF NO MOLECULE BY EXCITED-STATE. .

a
No+(x)
._

A B
4
44" 9-

r I

(a) @I (c)
. FIG. 1 Schematic energy diagram of NO molecule, relevant to autoionization. (a) The Av = 0 direct ion-
ization producing the v+ = 0 ion (the upward arrows show photoabsorption, while the downward
arrow shows the photoelectron energy. The shaded area in (b) and (c) schematically shows the
forbidden region of direct ionization.

occurs at a super-excited state. 3 Most important information deduced from photoelectron

spectra is the autoionization branching ratio of producing different electronic and vibrational’
states of ions, that cannot be obtained by other methods. The photoelectron branching
ratio should provide a clue to study the mechanisms of autoionization.
In our photoelectron studies of autoionization, we have selected special resonant
excited states, from which direct ionization to the ground state ion is forbidden in the sense
of one-electron ionization transition, and then we produced super-excited states through the
initial resonant excited states. In the present paper, I want to survey our recent photo-
electron spectroscopic studies of autoionization of NO molecule.

II. AUTOIONIZATION OF NO VIA RYDBERG A STATE

Concerning direct ionization, photoelectron spectra showing Av = 0 ionization transi-

tions have been observed for (2 + 2) resonant ionization of NO molecule via the v’ = O-3
vibrational levels of the Rydberg -A ‘C+ state. ‘ ” Some potential curves of NO are
schematically shown in Fig. 2. When NO molecule is excited to the v’ = 4 level of this
Rydberg state by the 374.7-nm two-photon energy, a total of three photons exceeds the
ionization threshold, but does not reach the v+ = 4 level of NO+(X). In other words, the
three-photon energy falls in the forbidden region (shaded area) in Fig. 1 (b).

- uii ,
 KATSUMIKIMURA 99

FIG. 2. Schematic potential curves relevant to resonant ionization of NO molecule; the Rydberg A, C, and
N states and the valence B and B’ states of the NO molecule, and the X state of NO+ ion.

In spite of the forbidden ionization transition, a weak MPI ion-current spectrum can be
observed in the laser wavelength region around 374 nm, attributable to the (2 + 1) resonant
ionization of the A *Z’ v’ = 4 level.8 Fig. 3 shows a photoelectron spectrum obtained at
the main ion-current peak (at 374.7 nm), indicating that the photoelectron spectrum largely
v+= 2

3 2 1 0.5 a2 0.1
Photoelectron Energy (eV)
FIG. 3. Photoelectron spectrum of autoionization of NO. obtained by (2 + 1) resonant ionization via the
Rydberg A v’ = 4 state, indicating four peaks. (Achiba et al., Ref. 3).
 100 STUDY OF ELECTRONIC AUTOIONIZATION OF NO MOLECULE BY EXCITED-STATE.

deviates from the normal Franck-Condon pattern of Av = 0 ionization transition. The v+ =

0. 1, 2 photoelectron bands in Fig. 3 are due to three-photon absorption, whereas the v+ = 4
band does result from four-photon absorption. This photoelectron spectrum indicates that
autoionization takes place at the three-photon energy level: and that the fourth-photon
absorption at this autoionizing level gives rise to the v+ = 4 ion.*
In general, the type of (n + 1) resonant ionization should be most important to study
autoionization, since there is no chance of accidental double resonance below the ionization
threshold. Anomalous photoelectron intensity distributions have also been observed for N,
molecule in (3 + 1) resonant ionization via the resonant b ’ llU state.’ In this case, the
anomalous photoelectron patterns have been discussed in terms of complex interactions
among the intermediate levels.

.
III. AUTOIONIZATION OF NO VIA VALENCE B STATE

The ionization transition producing the NO+ ground state from the non-Rydberg,
valence B zIT is electronically forbidden in the sense of one-electron transition. The
electronic configurations of the B 211 state of NO and the ground state (X ‘II) of the NO’
ion are shown in Table I. The lowest allowed ionic state produced by one-electron ioniza-
tion from the B 211 state is the a 3Z+ state, 6.5 eV above the ground state of NO+. There-
fore, the region below the a 3Z+ state of NO+ is the forbidden region (shaded in Fig. lc) in
this sense.

TABLE 1. Electronic configurations of

the electronic states of NO and NO+.

States Electron configuration

NOX 211 5s 17r4 27r’

A 2z1+ 5a2 l.rr4 3s
B ‘l-I 502 17T3 27r2
B’ ‘A 5a’ :lr427r2
c 2rI 502 1 n4 3p
NO+ X ‘C+ 5a2 17r4

The v’ = 9 vibrational level of the B ‘II state (hereafter denoted at B-9) has been
chosen as a resonant intermediate state to study autoionizatioq3 since there is no inter-
action between this level and any Rydberg states. If an MPI ion-current signal is produced
by one-photon absorption from B-9, it seems to be responsible.for autoionization. In fact,
a weak MPI ion-current spectrum can be observed in the region 369.0-370.5 nm, indicating
a number of peaks attributable to the rotational progressions. The rotational lines have

--..
 KATSUMI KIMURA 101

been explained partly in terms of a normal Boltzmann distribution at a temperature of

about 220 K.3 However, anomalous intensity enhancement occurs at several rotational
bands.
Two kinds photoelectron spectra have been observed at the rotational peaks of the (2 +
1) MPI ion-current spectrum in the B-9 region, as shown in Fig. 4’. The photoelectron
spectra (a) and (b) in Fig. 4 have been obtained by (2 + 1) absorption at the normal and the
anomalous ion-current peaks, respectively. The vibrational distribution of these photo-

2 1 0.8 0.4 02
Photoelectron Energy (eV)
FIG. 4. Photoelectron spectra of NO, obtained by (2 + 1) photon excitation via the B v’ = 9 state at (a) the
normal MPI ion-current peaks and (b) the anomalous one (Achiba et al., Ref. 3).

electron spectra show non-Franck-Condon behavior, suggesting that autoionization occurs in

the both cases. The v’ = 0, 1, 2 photoelectron bands mainly result from autoionizations
which occur at the three-photon energy levels, whereas a weak v+ = 6 photoelectron band is
produced by four-photon absorption. The appearance of the v+ = 6 band supports that
fourth-photon absorption is enhanced at the three-photon autoionizing discrete level.3
The possible valence super-excited states responsible for autoionization are considered
to be the B’ *lI and I *C+ states with the same electronic configuration.3 Electronic transi-
tion between these two states has been observed earlier in an emission study.” According
to theoretical and experimental studies, 11J2 the both B’ *A and I *Z+ states have repulsive
potential walls crossing the NO+(X *Zc’) potential curve near its minimum, as schematically
shown in Fig. 2.
If the three-photon energy just matches with a rotational level of a specific discrete
 102 STUDY OF ELECTRONIC ALTOIONIZATION OF NO MOLECULE BY EXCITED-STATE .

autoionizing state within several cm-‘, the corresponding MPI ion-cuxrent line should be
enhanced. Therefore, an anomalous-intensity ion-current line is expected to appear at each
accidental double resonance, overlapping with one of the normal rotational peaks. The
most probable candidate for the double-resonant state embedded in the ionization con-
tinuum is the v’ = 6 level of the Rydberg N ‘A state, which is allowed by one photon from
the B ‘II state.
The observed autoionization for the B 211 v’ = 9 state can be explained in terms of
electronic autoionization which involves electronic coupling between a dissociative portion
of the valence excited state and the ionization continuum.3 Generally speaking, in
electronic autoionization, photoelectron vibrational distribution is governed by a Franck-
Condon overlap of the vibrational wave functions between the autoionizing and the ionic
state.13*14 The important role of valence excited states in the autoionization process of NO
molecule at near the ionization threshold has been pointed out.‘5F16
On the basis of the autoionization mechanism, l6 the autoionization from the discrete
Rydberg N 2A v’ = 6 state, has been explained in terms of ‘indirect electronic coupling’
between this discrete state and the ionization continuum through a dissociative part of the
. valence excited B’ state.3 In other words, the Rydberg N 2A v’ = 6 state initially couples
electronically with the dissociative part of the B ’ 2A state with the same symmetry, and
then the dissociative B’ 2A state couples electronically with the ground-state ion. The
observed large deviation of the photoelectron spectra from the Av = 1 propensity rule,
which is widely accepted for vibrational autoionization, seems to be a strong experimental
evidence for the indirect autoionization mechanism.

IV. AUTOIONIZATION VIA HIGHER VALENCE B’ STATE

The higher valence excited state B ’ 2A (v’ = 3) has been selected as a resonant inter-
mediate in our (2 + 1) MPI experiments.r7 Again, one-p hoton direct ionization of this state
to the ground state ion is forbidden in the sense of one-electron Hamiltonian.
The photoelectron spectrum observed at the main rotational MPI peak of B’- 3 is
shown in Fig. 5, indicating a dominant peak due to v+ = 9 and weak peaks due to v+ = O-4.
The laser power dependences at the v+ = 2 and 9 peaks have been found to be different
(slopes of 2.2 and 1.6, respectively), suggesting that these peaks originate from different
ionization channels.
Franck-Condon factors between the B’-3 states and the ion ground state (NO+, X ‘C+)
have been calculated. l7 The calculated photoelectron vibrational distribution is schem-
atically shown in Fig. 6, in good agreement with the experimental one for the v+ = O-5
peaks. Therefore the weak photoelectron vibrational progression may be due to direct
ionization from B’-3;in spite of two-electron transition.
Since the slow photoelectron peak due to v+ = 9 (the energetically possible highest
vibrational level) in Fig. 5 cannot be explained by the direct ionization or the Av = -1 auto-
 KATSUMIKIMURA 103

9
m-L

2 1 a5
Pt-otoelectron Energy (eV)

FIG. 5. Photoelectron spectrum of NO obtained by (2+1) photon excitation via the B’ v’ = 3 state (Ref.
17).

i Ll-ll
V* 0 1 2 3 4 3 6 7 8 9
FIG. 6, Comparison of calculated and experimental Franck-Condon factors (Ref. 17) of the photo-
electron spectrum shown in Fig. 5. The calculated results are shown by dotted area.
 104 STUDY OF ELECTRONIC AUTOIONIZATION OF NO MOLECULE BY EXCITED-STATE,

ionization. the electronic autoionization proposed by Guisti-Suzor and Jungen16 is con-

sidered to occur through a repulsive portion of a neutral bound potential, as in the case of
the B 211 state. Further work on this is now in progress.r7

REFERENCES

1. K. Kimura, Adv. Chem. Phys. 60, 16 1 (1984).

2. K. Kimura, Intern. Rev. Phys. Chem. 6, 195 (1987).
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4. Y. Achiba and K. Kimura, Chem. Phys., in press.
5. J. C. Miller and R. N. Compton, J. Chem. Phys. 75, 22 (1981).
6. J. C. Miller and R. N. Compton, Chem. Phys. Lett. 93,453 (1982).
7. J. Kimman, P. Kruit and M. J. van der Wiel, Chem. Phys. Lett. 88,576 (1982).
8. Y. Achiba and K. Kimura, J. Chem. Sot. Japan (in Japanese), 1529 (1984).
9. S. T.Pratt, J. L. Dehmer and P. M. Dehmer, J. Chem. Phys. 80, 1706 (1984).
. 10. K. P. Huber, Phys. Acta 37, 329 (1964).
11. J. N. Bardsley, Planet. Space Sci. 31, 667 (1983).
12. E. Miescher, Can. J. Phys. 54, 2074 (1976).
13. J. Berkowitz, “P hotoabsorption, Photoionization, and Photoelectron Spectroscopy”
(New York, Academic, 1979).
14. J. H. D. Eland, J. Chim. Phys. 77, 613 (1980).
15. Ch. Jungen, Can, J. Phys. 44, 3197 (1966).
16. A. Guisti-Suzor and Ch. Jungen, J. Chem. Phys. 80, 986 (1984).
17. M. Takahashi, K. Okuyama and K. Kimura, to be published.