J. Mass Spectrom. Soc. Jpn.

Vol. 57, No. 6, 2009

REVIEW
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Fundamentals of Mass Spectrometry
ῌBasic Understanding of Penning Ionizationῌ
Masatoshi U@6> 

 Department of Applied Physics, Tokyo University ofAgriculture and Technology, Koganei, TOKYO, JAPANPenning ionization, one of the fundamental chemical reactions involved in ionized gases, is recently
demonstrated to facilitate a new type soft ionization source with a high-e$ciency in mass spectrometry. In thisreview I present indispensable physico-chemical understanding of Penning ionization to design and to operate
Penning ionization ion source.
(Received June 1, 2009; Accepted June 1, 2009)" #@.3v A῎ KID L

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Correspondence to: Masatoshi U@6>, Department of Applied
Physics, Tokyo University of Agriculture and Technology,
Naka-cho 2῍24῍16, Koganei, Tokyo 184῍8588, JAPAN,
e-mail: ukai3@cc.tuat.ac.jp    ¸184῍8588 +¹º»¼½ 2῍24῍169:;<=5nl#®¯.x!£nv£ )9:;<=5"rU=U=4 ¤£nv£°a4¥D0A'£nv±#E. *0*²³#´µ].@|#¶.
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EA῍ (eV)

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1

He

2 P
2 3P
2 1S
2 3S

21.21720.96420.61519.819Ne

3s 1P13s 3P03s 3P13s 3P2Ar

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' (
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2 PR1 S
2 3 P R 2 3S

58.43 nm
1008.3 nm

16.84816.71616.671
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3s 1P1 R 2p6 1S0

73.59 nm

3s3 P1 R 2p6 1S0

74.37 nm11.82811.723
11.624
11.548V  W ' (W V  W ' (W 

4s 1P1 R 3p6 1S0

104.82 nm

4s 3P1 R 3p6 1S0

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c 2007 Taylor & Francis Group7'
IJK. 56| 28 :$¹º.QT¸' ῌFig. 10.

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Fig. 9g5 0&( 6| 1)}5), 28) 3~qr7?

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Fig. 10

[X
3' (:;<,#?,#e" 5He(2 1 S) @&He(2 3S)7 :$/[i# !)* @&' 

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' BcCD&?@'^4( IJK_!J> `a

( bcd0 !e")*f# :;( :$$ῑ ῐ 'm-E ¡F¢GH£¤dI)¥ :$¦( §*% 4&28), 32)'

/@w3¨©ª.&«=' =( ?-JKXL¬M­ 

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KX^¶.&«X/ ·T¸.¹º&«=' M­»-UVI) 'm:OPGQRn& M:o(4(῍ 403 ῍z{3¼W.

M. Ukai 
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ῌ
19)

1) A. Niehaus, Adv. Chem. Phys., 45, 399 (1981).
2) A. Yencha, “Electron Spectroscopy, ῌTheory, Techniques, and Applicationsῌ,” ed. by C. R. Brundle and A.
D. Baker, Vol. 5, Academic, New York (1984), p. 197.
3) P. E. Siska, Rev. Mod. Phys., 65, 337 (1993).
4) M. Ukai and Y. Hatano, “Gaseous Electronics and Its
Applications,” ed. by R. W. Crompton, M. Hayashi, D. E.
Boyd, and T. Makabe, KTK Scientiﬁc, Tokyo (1991), p.
51.
5) M. Ukai and Y. Hatano, “Charged Particles and Photon
Interactions with MatterῌChemical, Physico Chemical,
and Biological Consequences with Applications,” ed. by
A. Mozumder and Y. Hatano, Marcel Dekker, New York
(2004), p. 121.
6) Y. Harada, S. Msasuda, and H. Ozaki, Chem. Rev., 97,
1897 (1997).
7) J. H.    !"#$%&'($) *+,-./01- (2007)
8) K. Hiraoka, J. Mass Spectrom. Soc. Jpn., 53, 60 (2005).
9) T. Iwama, M. Hirose, I. Yazawa, H. Okada, and K. Hiraoka, J. Mass Spectrom. Soc. Jpn., 54, 227 (2006).
10) K. Hiraoka, H. Furuya, S. Kambara, S. Suzuki, Y. Hashimoto, and A. Takamizawa, Rapid Commun. Mass Spectrom., 20, 3213 (2006).
11) 2345 67#$8 116, 223 (1996).
12) 9:;< =>#?@A BCDEF 24, GH (1989),
p. 119.
13) IJKL J. Mass Spectrom. Soc. Jpn., 57, 387 (2009).
14) 2345 M#NOP 42, 215 (1989).
15) 2345 QRAM# 57, 13 (1994).
16) Y. Hatano, Phys. Rep., 313, 109 (1999).
17) R. D. Levine and R. B. Bernstein, “Molecular Reaction
Dynamics and Chemical Reactivity,” Oxford Univ.
Press, Oxford (1987).

20)
21)
22)
23)

24)

25)
26)
27)
28)
29)
30)
31)

32)

M. Ukai, H. Yoshida, Y. Morishima, H. Nakazawa, K.
Shinsaka, N. Kouchi, and Y. Hatano, J. Chem. Phys., 88,
3623 (1988).
Y. Morishima, M. Ukai, N. Kouchi, and Y. Hatano, J.
Chem. Phys., 96, 8187 (1992).
M. Kitajima, K. Hidaka, H. Kusumori, M. Ukai, N.
Kouchi, and Y. Hatano, J. Chem. Phys., 100, 8072 (1994).
H. Koizumi, M. Ukai, Y. Tanaka, K. Shinsaka, and Y.
Hatano, J. Chem. Phys., 85, 1937 (1986).
Y. Morishima, H. Yoshida, M. Ukai, K. Shinsaka, N.
Kouchi, and Y. Hatano, J. Chem. Phys., 97, 3180 (1992).
H. Fukuzawa, M. Murata, N. Kiyoto, T. Mukai, Y. Fukuchi, D. B. Khadka, M. Ukai, T. Odagiri, K. Kameta, N.
Kouchi, and Y. Hatano, J. Chem. Phys., 118, 70 (2003).
A. Merz, M.-W. Ruf, H. Hotop, M. Movre, and W. Meyer,“The Physics of Electronic and Atomic Collisions,” ed.
by T. Andersen, et al., AIP Press, New York (1994), p.
852.
K. Katsuura, J. Chem. Phys., 42, 3771 (1965).
T. Watanabe and K. Katsuura, J. Chem. Phys., 47, 800(1967).
T. Watanabe and M. Stener, J. Chem. Phys., 121, 9948
(2004).
N. Kishimoto and K. Ohno, Int. Rev. Phys. Chem., 26, 93(2007).
K. Ohno, H. Mutoh, and Y. Harada, J. Am. Chem. Soc.,
105, 4555 (1983).
K. Ohno, T. Takami, K. Mitsuke, and T. Ishida, J. Chem.
Phys., 94, 2675 (1991).
H. Yoshida, M. Kitajima, H. Kawamura, K. Hidaka, M.
Ukai, N. Kouchi, and Y. Hatano, J. Chem. Phys., 98, 6190
(1993).
S. Maeda, M. Yamazaki, N. Kishimoto, and K. Ohno, J.
Chem. Phys., 120, 781 (2004).

Keywords: Penning-ionization cross section, De-excitation
cross section, Electron-exchange interaction, Dipole-dipole interaction, Ionization quantum yieldῌ 404 ῌ