Fundamentals of Mass Spectrometry Gas Phase Ion/Molecule Reactions

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1 J. Mass Spectrom. Soc. Jpn. Vol. 58, No. 3, 2010 REVIEW 7 Fundamentals of Mass Spectrometry Gas Phase Ion/Molecule Reactions Kenzo H>G6D@6 Kofu, YAMANASHI, JAPAN Clean Energy Research Center, University of Yamanashi, The ionization is the first step for the mass spectrometry. The ion/molecule reactions play major roles not only in the gas-phase chemical ionization but also in the ionization processes in condensed phases, e.g., secondary ion mass spectrometry (SIMS), matrix-assisted laser desorption/ionization (MALDI), electrospray ionization (ESI), field desorption (FD), and field ionization (FI). In general, the mass spectra obtained by various ionization methods reflect the outcome of complex ion/molecule reactions taking place in the respective ionization method. Thus, fundamental knowledge on the ion/molecule reactions is indispensable to make the mass spectrometry as the superb analytical technique. In this chapter, the fundamentals of ion/molecule reactions will be described. (Received January 27, 2010; Accepted January 28, 2010) 1. H 3 Thomson ) H 3 Eyring H 3 Scandal of modern chemistry 2) H H (1), (2) 3), 4) CH 4 CH 4 CH 5 CH 3 (1) CH 3 CH 4 C 2 H 5 H 2 (2) 70 ev CH 4 CH 3 CH 5 C 2 H 5 CH 5 C 2 H 5 (1), (2) Correspondence to: Kenzo H>G6D@6, Clean Energy Research Center, University of Yamanashi, Takeda, Kofu, Yamanashi , JAPAN, hiraoka@yamanashi. ac.jp CH 5 C 2 H 5 Field Munson (1), (2) Field CH 5 C 2 H 5 5) (electron ionization: EI) chemical ionization (CI) 6) CI CI EI M m/z M 1 CI CI 7) CI APCI (atmospheric-pressure chemical ionization) CI EI 93

2 K. Hiraoka 8), 9) 1980 CI APCI CI 2. CI 1 k n k n 2.1 CH 5 M [M H] M (m D ) N 2 CH 4 m M k L Langevin 10), 11) (3) k L 2pe(a/m) 1/2 (3) Langevin a m [mm/(m M)] AÕ 3 (u) Langevin (4) k L (a/m) 1/2 cm 3 molecule 1 s 1 (4) (1) a 2.56 AÕ /(16 16) 8 u k L cm 3 molecule 1 s 1 ( cm 3 molecule 1 s 1 ) Langevin HCl H 2 O H d Cl d average dipole orientation (ADO) 12), 13) (5) k ADO (2pe/m 1/2 )[a 1/2 cm D (2/pkT) 1/2 ] (5) 1 (3) 2 m D k Boltzmann T (K) c Fig. 1 m D /a 1/2 0 1 locking a AÕ 3 m (u), m D (Debye) cgs esu cm SI C m (5) (6) k ADO (a/m) 1/ c m D 94

3 Table 1. m (Debye) a (AÕ 3 ) Fig. 1. locking 12) 1973, Elsevier (2780/Tm) 1/2 cm 3 molecule 1 s 1 (6) Average dipole orientation (7) CH 5 NH 3 CH 4 NH 4 (7) a 2.16 AÕ 3 m D 1.47 Debye, m 17 17/(17 17) 8.5 u, c m D /a 1/2 1.47/(2.16) 1/2 1 Fig. 1 c 0.22 (6) 300 K k ADO cm 3 molecule 1 s 1 ( cm 3 molecule 1 s 1 ) Table 1 14) 17) (6) A B A B k L k ADO 18) O d d C d O d 19) k L k ADO Franck Condon 20) k L k ADO k L k ADO k n 1 n (molecule/ cm 3 ) He Ne Ar Kr Xe H D O N CO NO HCl HBr CO CS H 2 O N 2 O H 2 S SO CH CCl C 2 H C 2 H n-c 4 H i-c 4 H C 6 H NH H 2 CO CH 3 OH (CH 3 ) 2 CO (sticky collision) 1 DH, DH : 95

4 K. Hiraoka ,800 1 (RE: recombination energy) 21) ionization energy: IE Ar C 6 H 6 Ar C 6 H 6, IE IE(Ar) IE(C 6 H 6 ) ev C 6 H 6 C 6 H 6 RE Franck Condon 22) Horning (APCI) 23), 24) CI N 2 e N 2 2e (8) N 2 2N 2 N 4 N 2 (9) N 4 H 2 O H 2 O 2N 2 (10) H 2 O H 2 O H 3 O OH (11) H (H 2 O) n 1 H 2 O N 2 H (H 2 O) n N 2 (12) N 4 C 6 H 6 C 6 H 6 2N 2 (13) C 6 H 6 M M C 6 H 6 (14) MH C 6 H 5 (15) N 2 He, Ar, gas chromatography (GC) gas chromatography chemical ionization mass spectrometry (GC-CIMS) (RE) (IE) 25) 9.2 ev NO 26) 31) Trimethylsilyl (TMS) M 28) (7) k L (4) T k ADO (6) 1/T 1/2 2 32) (4) (6) (H ) hydride ion, s-c 3 H 7 i-c 4 H 10 t-c 4 H 9 C 3 H 8 (16) t-c 4 H 9 i-c 5 H 12 t-c 5 H 11 i-c 4 H 10 (17) H electron a$nity: EA 0.75 ev He H (18) H H CH 4 H H C CH 3 H 2 (18) H H H CH 4 C H s (18) ) CH 3 H 2 H 34) (18) tight complex 32), 35), 36) tight complex tight complex 96

5 tight complex complex k (17) k 640 K cm 3 molecule 1 s 1 1, K cm 3 molecule 1 s K cm 3 molecule 1 s 1 (19) k 300 K, 640 K cm 3 molecule 1 s 1 t-c 4 H 9 (C 2 H 5 ) 3 N (C 2 H 5 ) 3 NH i-c 4 H 8 (19) (20) 3 M A B M kf AB M (20) A B kc kb [AB ] (21) [AB ]M ks AB M (22) A B 3 A B H 3 2 (20) (21), (22) k c A B (collision), k b [AB ] (back dissociation), k s [AB ] M [AB ] (stabilization) k c k s k L k ADO (21), (22) [AB ] (20) (23) k f k ck s [M] k b k s [M] (23) 3 M 3 M [AB ] 3 M A B k b k s [M] k f (24) k f k ck s [M] k b k t [M] (24) (20) [A ], [B] [M] [M] 3 k t 37) 3 H 3 O (25) k t T 4 38) H 3 O H 2 O CH 4 H 3 O (H 2 O) CH 4 (25) k t /T 4 cm 6 molecule 2 s 1 (26) A B [AB ] [AB ] 3 (22) (24) k b k t k s 3 M M [AB ] (V) M (T) V T M V T M (V V) (V R) k s k s (24) k t 39, 40 Fig. 2 [AB ] 3 M k b k s [M] (23) (27) k f k c (27) k f A B k c (20) 2 Fig. 2. (E), (V), (R), (T) 97

6 K. Hiraoka 2 (pseudo 2 nd order reaction) k b k s [M] k b k s [M] N 2 N 2 N 4 O 2 O 2 O 4 41), NH 4,CH 3 NH 3 (CH 3 ) 2 NH k f 3 M (23) 42) 44) (21), (22) AB e AB (28) AB A B (29) AB M AB M (30) AB e A B e (31) AB X AB X (32) CI (electron capture) O 2 e O 2 (33) O O (34) SF 6 e SF 6 (35) SF 5 F (36) CCl 4 e Cl CCl 3 (37) Fig. 3 O 2 O 2 45) O 2 O 2 O 2 (v 0) 0.08 ev O 2 (v4) 0.08 ev O 2 (v4) O 2 O 2 (v4) Fig. 3. Fig. 4. O 2 (X 3 g ) O 2 (X 2 P g ) , Elsevier s a (e max ) (cm 2 ) e max (ev) John Wiley & Sons O 2 O 2 O 2 (v4) 3 M v3 O 2 e O 2 (38) O 2 M O 2 M (39) 98

7 Table 2. (ev) H 0.75 O 1.46 F 3.4 Cl 3.62 Br 3.37 I 3.07 NO NO NO N 2 O 0.22 O O OH 1.83 SCN 2.17 SF SF O 2 O (29) Fig. 4 AB e A B (s amax (cm 2 )) (e MAX (ev)) 46) (cm 2 ) Fig. 3 O 2 (v 0) O 2 (v0) 0.5 ev Table 2 47) S N 2 48) 50) H, H 2, H 2 51) CI APCI matrix-assisted laser desorption/ionization (MALDI), secondary ion mass spectrometry (SIMS), electrospray ionization (ESI) ) Viggiano 1,100 9, DH DH DS DGDHTDS, DG (RE) (IE) AH B A BH B A A BH AH B A B A B C D, DH DH f DHDH f (C ) DH f (D) DH f (A ) DH f (B) 99

8 K. Hiraoka 56 (NIST Chemistry WebBook, URL: nist.gov/chemistry/ ). 3.2 CI, APCI ion cyclotron resonance, ICR Torr kev ms ms ms ICR 10 2 Torr ( 5 ms) 300 1,000 ms K K DG DH DS (40) van t Ho# RT ln K DGDHTDS (40) (40) (41) 1/T van t Ho# DH, 1/T 0 DS ln K DH RT DS R (41) CI APCI MALDI SIMS (42) K (43) B 1 H B 2 B 1 B 2 H (42) K [B 1 ][B 2 H ]/[B 1 H ][B 2 ] (43) DG (40) (42) B 1 B 2 (proton a$nity: PA) PA(B 1 ) PA(B 2 ), DH (40) (42) DG van t Ho# DH (42) DS Lau 60) (42) DS s (44) DS rotsym R ln s(b 1H )s(b 2 ) s(b 2 H )s(b 1 ) (44) K DG (44) DS (42) DS 8 12 J/K mol DGDH DG DHPA(B 1 ) PA(B 2 ). PA PA H 2 O s PA H 2 O NH 3 p n non-bonding PA NH 3 n Table 3 61 PA PA H 2 H 3 CO C O PA kj/mol COH HCO CO (highest occupied molecular orbital: HOMO) 5s C CO C (C d O d ), 5s (HOMO) C C 2 H 4 C 2 H 5 p (HOMO) H 2 CH CH 2 H 3 C CH 2 H 3 O NH 3 N (HOMO) NH 4 NH 4 H 100

9 Table 3. (kj/mol) (kj/mol) C 4 H 10 O n-c 4 H 9 OH He He C 4 H 10 O i-c 4 H 9 OH Ne Ne C 4 H 10 O (C 2 H 5 ) 2 O Ar Ar C 6 H 6 O C 6 H 5 OH Kr Kr C 12 H 24 O 6 18-Crown Xe Xe NH 3 NH H 2 H CH 5 N CH 3 NH O 2 O C 2 H 7 N (CH 3 ) 2 NH N 2 N C 3 H 9 N (CH 3 ) 3 N CO CO at C 594 C 2 H 3 N CH 3 CN CO CO at O C 2 H 7 N C 2 H 5 NH CO 2 CO C 4 H 5 N Pyrrole CS 2 CS C 4 H 9 N Pyrrolidine NO NO C 5 H 5 N Pyridine 930 N 2 O N 2 O at N C 5 H 11 N Piperidine 954 N 2 O N 2 O at O C 6 H 7 N C 6 H 5 NH NO 2 NO C 9 H 7 N Quinoline SO 2 SO O 3 O CH 5 N 3 Guanidine H 2 S H 2 S 705 C 2 H 5 NO 2 Glycine C 3 H 7 NO 2 A-Alanine CH 4 CH C 3 H 7 NO 2 S A-Cysteine C 2 H 6 C 2 H C 3 H 7 NO 3 A-Serine C 2 H 4 CH 2 CH C 4 H 4 N 2 O 2 Uracil C 2 H 2 C 2 H C 4 H 5 N 3 O Cytosine C 3 H 8 C 3 H C 4 H 7 NO 4 A-Aspartic acid C 3 H 6 CH 3 CH CH C 4 H 8 N 2 O 3 A-Aspargine 929 C 3 H 4 H 2 C C CH C 4 H 9 NO 3 A-Threonine C 3 H 4 H 3 CC CH 748 C 5 H 5 N 5 Adenine C 4 H 10 i-c 4 H C 5 H 5 N 5 O Guanine C 6 H 6 C 6 H C 5 H 6 N 2 O 2 Thymine C 7 H 8 C 6 H 5 CH C 5 H 9 NO 2 A-Proline C 10 H 8 o-xylene 796 C 5 H 9 N 3 Histamine C 10 H 8 p-xylene C 5 H 10 N 2 O 3 A-Glutamine C 12 H 10 Biphenyl C 5 H 11 NO 2 A-Valine C 14 H 10 Anthracene C 5 H 11 NO 2 S A-Methionine C 24 H 12 Coronene C 6 H 6 N 2 O Nicotinamide C 6 H 9 N 3 O 2 A-Histidine 988 H 2 O H 2 O 691 C 6 H 13 NO 2 A-Leucine H 2 O 2 H 2 O C 6 H 13 NO 2 A-Isoleucine CH 2 O H 2 CO C 6 H 14 N 2 O 2 A-Lysine 996 CH 4 O CH 3 OH C 6 H 14 N 4 O 2 A-Arginine 1051 CH 2 O 2 HCOOH 742 C 9 H 11 NO 2 A-Phenylalanine C 2 H 6 O C 2 H 5 OH C 9 H 11 NO 3 A-Tyrosine 926 C 2 H 6 O CH 3 OCH C 9 H 12 N 2 O 6 Uridine C 2 H 4 O 2 CH 3 COOH C 9 H 13 N 3 O 5 Cytidine C 3 H 8 O n-c 3 H 7 OH C 10 H 13 N 5 O 2 Guanosine C 3 H 8 O i-c 3 H 7 OH 793 C 10 H 13 N 5 O 4 Adenosine C 4 H 4 O Furan C 11 H 12 N 2 O 2 A-Tryptophan C 4 H 8 O Tetrahydrofuran (NH 3 CH 3 NH 2 (CH 3 ) 2 NH (CH 3 ) 3 N), PA Table 3 PA PA (1,051 kj/mol) PA (986.3 kj/mol) PA PA 101

10 K. Hiraoka 3.4 AH AH B A BH [CH 3 COOH H] CH 3 COOH CH 3 COO H H 2 H H 3 H 2 H 2H H CH 3COOH H 2 H CH 3COOH H 2 CH 3COO CH 3COOH H CH 3COO CI (45) A 1 A 2 H A 1 H A 2 (45) DH 45 A H D(A H) A EA(A ) (46) DH 45 D(A 2 H) EA(A 2 ) D(A 1 H) EA(A 1 ) (46) A PA(A ) DH 45 (47), (48) IE(H) DH 45 PA(A 2 ) PA(A 1 ) (47) PA(A ) D(A H) EA(A) IE(H) (48) (48) A H AH, D(A H) EA(A) AH H AH (45) DH Table 4. [D EA] [D EA] (kj/mol) H H 2 O 322 CH 3 OH 264 C 2 H 5 OH 256 DMSO 255 CH 3 CN 250 (CH 3 ) 2 CO 236 HF 235 H 2 S 161 C 6 H 5 OH 151 CH 3 COOH 146 HCOOH 132 C 6 H 5 COOH 112 HCl 84 CF 3 COOH 38 HBr 42 HI 3 62) 72) (D EA) Table 4 CI A AH (45) O 2 e O O (49) O 2 e M 3 O 2 M 3 (50) H 2 O e (6.5 ev) OH H (51) CH 4 e (10 ev) H CH 3 C 2 H,C 2,C, etc. (52) NH 3 e H NH 2 or NH 2 H (53) CI CI CCl 4,NF 3,CH 3 ONO CCl 4 e Cl CCl 3 (54) NF 3 e F NF 2 (55) CH 3 ONO e CH 3 O NO (56) Cl, F, CH 3 O CCl 3 Cl CCl 4 CCl 3 Cl, 297 kj/mol Cl EA 349 kj/mol (54) kj/ mol Table 4 HI HI I I HI HI H,OH,CH 3 O H 2,H 2 O, CH 3 OH OH,CH 3 O H 2 O, CH 3 OH OH H 2 CH 4 N 2 O 73) N 2 O O O H 2 CH 4 OH 102

11 Table 5. DH (kj/mol) DS (J/mol K) n 1 n 2 n 3 n 4 n 5 n 6 n 7 n 8 n 9 H 3 (H 2 ) n N 2 (N 2 ) n O 2 (N 2 ) n He (He) n NO (NO) n H 3 O (H 2 O) n CH 3 OH 2 (CH 3 OH) n H (CH 3 COCH 3 )(CH 3 COCH 3 ) n H (C 2 H 5 OH)(H 2 O) n t-c 4 H 9 (H 2 O) n Li (H 2 O) n Na (H 2 O) n K (H 2 O) n Rb (H 2 O) n Cs (H 2 O) n F (H 2 O) n Cl (H 2 O) n Br (H 2 O) n I (H 2 O) n F (CO 2 ) n CI 73) 75) F (55) HF (Table 4), F (45) HCl Cl RH (57) DG DH DS DH f 56 NIST (URL: ). R 1 R 2 H R 1 H R 2 (57) (57) DS 4 12 J/mol K (57) DH DG DGDHTDS DS DGDH C 2 H 5 i-c 4 H 10 C 2 H 6 t-c 4 H 9 DH 56 DH f DH (kj/mol) [DH f (C 2 H 6 ) DH f (t-c 4 H 9 )] [DH f (C 2 H 5 ) DH f (t-c 4 H 10 )] [( 84) (693)] [(901) ( 134)]158 kj/mol 103

12 K. Hiraoka DH C 2 H 5 i-c 4 H 10 t-c 4 H 9 C 2 H 5 (2) CH 5 C 2 H 5 (1) (2) PA (543.5 J/mol) PA (625.7 kj/mol) CH 5 C 3 H 8 CH 4 C 3 H 9 C 3 H 9 i-c 3 H 7 H 2 PA (680.5 kj/mol) PA (625.7 kj/mol) C 2 H 5 C 3 H 8 C 2 H 5 i-c 3 H 7 C 2 H 5 C 3 H 8 C 2 H 6 i-c 3 H 7 i-c 3 H (20), (21), (22) 3 mtorr CI Torr (58) A S M A S M (58) A S n 1 S M A S n M (59) A S n B A S n 1 B S (60) M: 3 S: (60) S B 3 (60) A S n 1 B S A S n Table 5 ( DH (kj/mol)), ( DS (J/mol K)) (URL: ) (a) H 3,CH 5,C 2 H (b) H 3 H 2 H 3 (H 2 ) n H 3 (H 2 ) 3 (H 2 ) 3 (H 2 ) 2 (shell) H 3 6 H 2 H 3 H 2 (c) N 2 N 2 (N 2 ) 2 (N 2 ) n N 4 D 2h (d) O 2 O 2 O 2 (O 2 ) 3 (O 2 ) n (O 2 ) 2 (O 2 ) n (e) O 2 N 2 O 2 (N 2 ) 4 (N 2 ) n N 2 O 2 p lobe (f) Rg (Rg 3 ) (Rg) n Rg Rg 3 (g) NO (NO) n n n NO n NO (NO) n (h) H 2 O H H (S) n n H n 2 S H S H 3 C C N H N C CH 3 n 3 (i) F (CO 2 ) n n 1 FCOO n 2 Cl (CO 2 ) n n

13 DS (J/mol K) (Table 5) DS 120 (J/mol K) DS 80 (J/mol K) 58), 59) H 2 O H 2 O PA H 2 O PA H 3 O H H 2 O PA Table 3 H H 3 O H 2 O H 3 O (H 2 O) n n n Table 5 C 2 H 5 OH 2 DH n 1, n n 4 n 4 5 n 4 5 C 2 H 5 OH 2 (H 2 O) n H 3 O (H 2 O) n 1 (C 2 H 5 OH), n n C 2 H 5 OH 2 H 3 O t-c 4 H 9 t-c 4 H 9 H 2 O t-c 4 H 9 OH 2 t-c 4 H 9 OH t- Table 5 n 1 2 t-c 4 H 9 OH 2 H 2 O H 3 O (t-c 4 H 9 OH), t-c 4 H 9 OH H 3 O (H 2 O) n i-c 4 H 8 CI A (S) n H 2 O NH 3 H 3 O (H 2 O) n NH 4 (NH 3 ) n H 3 O NH 4 CI Table 5 H 3 O (H 2 O) n n DH n 1, n 1 PA 691 kj/mol (Table 3) n 1, 2, 3, PA 837, 922, 997 kj/mol (Table 5) n kj/mol NH 3 PA 854 kj/mol H 3 O (H 2 O) (Table 3). (60) H 3 O (H 2 O) (CH 3 ) 2 CO [(CH 3 ) 2 CO H 2 O H] H 2 O M w m/z M w CI CI Torr 1 mtorr H 3 O (H 2 O) n n (373 K) H 3 O H 3 O (H 2 O) Table 5 H 3 O H 2 O H 3 O (H 2 O), DH DS kj/mol J/mol K DG DHTDS146, ,227 J/mol RT ln K ln K K K (atm) atm K 1 mtorr P(H 2 O) 10 3 /760 K {I[H 3 O ]/ I[H 3 O (H 2 O)]}/P(H 2 O) P(H 2 O) I[H 3 O ]:I[H 3 O (H 2 O) 1 ] 1 : H 3 O (H 2 O) n n H 3 O : H 3 O (H 2 O) : H 3 O (H 2 O) 2 :H 3 O (H 2 O) 3 :H 3 O (H 2 O) 4 1: : : : H 3 O (H 2 O) (573 K) H 3 O :H 3 O (H 2 O) : H 3 O (H 2 O) 2 :H 3 O (H 2 O) 3 :H 3 O (H 2 O) 4 1 : 7.4 : : :

14 K. Hiraoka H 3 O (H 2 O) n H 3 O H 3 O (H 2 O) CI (61) 163 kj/mol H 3 O NH 3 NH 4 H 2 O (61) 163 kj/mol H 2 O 1.84 NH 4 NH 4 (H 2 O) CI Cl 76) NO 30), 31) H 3 O (H 2 O) n n 10 K Laval Table 5 n 1 Li F Li M Li M 77), 78) Li M Li M CI CI Li M Li M M M 4. C I 4.1 CI 1ppm PA AH B A BH, A/B 10 6,[BH ]/[AH ] 0.01 AH 1 BH 200 DGRT ln K ln kj/mol DS0 J/ mol K DGDH 1ppm PA 36 kj/mol 4.2 CI (42) B 2 H (45) A 1 H B 1 H B 2 B 1 B 2 H (42) A 1 A 2 H A 1 H A 2 (45) H Hunt 79), In 106

15 the case of an exothermic gas phase proton transfer reaction proceeding through a short-lived ion molecule complex, the energy liberated remains largely in the product containing the newly formed bond. (42) B 2 H B 2 H (45) A 1 H A 2 CI OH A n 1 k (cm 3 / molecule s) n (cm 3 ) n k n (s 1 ) (62) n (cm 3 ) n (cm 3 ) P (Torr)/T (K) (63) (42) (45) 1 1 t (s) (64) t ln 2/k n 0.693/k n (s) (64) t (s) 2 1 1ppm 5 Torr, 760 Torr 1 t (s) s s 5 Torr CI ms 1ppm APCI ms 1 APCI CI ppb ppt / / / Torr CI CI ( 10 5 Torr) (EI) EI EI EI CI EI EI CI, APCI ppt PA EA PA EA 4.4 (l D ) l D l D (cm) 5/P (mtorr) (65) 1 1 Torr, 10 3 Torr l D cm, cm, 5 cm 1 mtorr 5cm 400 m/s ,10 7,10 4 E 107

16 K. Hiraoka v d (drift velocity) E v d E v d me (66) (66) m (cm/s)/(v/cm), m (cm 2 /V s) 1 V/cm (cm/s) P (Torr) T (K) m m 0 (67) m 0 m(p/760) (273/T) (67) 0, 1 (760 Torr) v d P (Torr) T (K) (cm 2 /V s) 0, 1 He (He) : 10.8, Ne (Ne) : 4.4, Ar (Ar) : 1.63, Kr (Kr) : 0.93, Xe (Xe) : 0.63 Ar 1 V/cm 0, 1 Ar 1.63 cm/s KE ion v d Wannier 80), 81) KE ion (1/2)mv 2 d (1/2)M b v 2 d (3/2)kT (68) m M b k Boltzmann T (68) v d 2 (3/2)kT, (1/2)mv d (1/2)M b v 2 d 1 1,000 V/cm Ar (66) 1,800 cm/s APCI 1cm 1/v d s Ar Ar t s 10 9 cm 3 /molecule s (64) n n cm Torr 50 ppb 1,000 V/cm ppt APCI 1,000 V/cm (68) m M b / kg, v d 18 m/s, k J/K, T 300 K, (68) KE ion ( ) J 301 K, 1,000 V/cm 760 Torr 1K 1 Torr 10 V/cm v d cm/s s n n cm 3 1 Torr 300 ppm APCI APCI ( ) J 300 K 360 K, 1 Torr 10 V/cm 60 K (65) CI (collision-induced dissociation: CID) N 2 CID CID 5. (1), (2) 1950 CI APCI MALDI, surface-assisted laser desorption/ionization (SALDI), SIMS, 10 3 Torr 108

17 1) J. J. Thomson, Phil. Mag., 24, 209 (1912). 2) G. S. Handler and J. R. Arnold, J. Chem. Phys., 27, 144 (1957). 3) V. L. Tal rose and A. K. Lyubimova, Dokl. Akad. Nauk. SSSR, 88, 909 (1952). 4) D. P. Stevenson and D. O. Schissler, J. Chem. Phys., 23, 1353 (1955). 5) M. S. B. Munson and F. H. Field, J. Am. Chem. Soc., 87, 3294 (1965). 6) M. S. B. Munson and F. H. Field, J. Am. Chem. Soc., 88, 2621 (1966). 7) J. H. (2009). 8) 28, 185 (1980). 9) P. Kebarle, Ann. Rev. Phys. Chem., 28, 445 (1977). 10) P. Langevin, Ann. Chim. Phys., 5, 276 (1905). 11) G. G. Gioumousis and D. P. Stevenson, J. Chem. Phys., 29, 294 (1958). 12) T. Su and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys., 12, 347 (1973). 13) L. Bass, T. Su, W. J. Chesnavich, and M. T. Bowers, Chem. Phys. Lett., 34, 119 (1975). 14) E. W. Rothe and R. B. Bernstein, J. Chem. Phys., 31, 1619 (1959). 15) R. J. W. LeFevre, Adv. Phys. Org. Chem., 3, 1 (1959). 16) R. D. Nelson, Jr., D. R. Lide, Jr., and A. A. Maryott, NSRDS-NBS 10, (1967); URL: nist. gov/ srd/nsrds/nsrds-nbs-10. pdf. 17) A. L. McClellan, Tables of Experimental Dipole Moment, W. H. Freemen, San Francisco, Calif. (1963). 18) T. Su and M. T. Bowers, J. Chem. Phys., 58, 3027 (1973). 19) T. Su and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys., 17, 309 (1975). 20) W. E. Farneth and J. I. Brauman, J. Am. Chem. Soc., 98, 7891 (1976). 21) E. Lindholm, Ion Molecule Reactions, Vol. 2, ed. by J. L. Franklin, Plenum Press, New York (1972), p ) M. Chau and M. T. Bowers, Int. J. Mass Spectrom. Ion Phys., 24, 191 (1977). 23) E. C. Horning, M. G. Horning, D. I. Carroll, I. Dzidic, and R. N. Stillwell, Anal. Chem., 45, 936 (1973). 24) E. C. Horning, M. G. Horning, D. I. Carroll, R. N. Stillwell, and I. Dzidic, Life Science, 13, 1331 (1973). 25) B. Munson, Anal. Chem., 49, 772A (1977). 26) N. Einolf and B. Munson, Int. J. Mass Spectrom. Ion Phys., 9, 141 (1972). 27) D. F. Hunter and J. F. Ryan, J. Chem. Soc., Chem. Commun., 620 (1972). 28) B. L. Jelus, B. Munson, and C. Fenselau, Biomed. Mass Spectrom., 1, 96 (1974). 29) D. F. Hunt, C. N. McEwen, and T. M. Harvey, Anal. Chem., 47, 1730 (1975). 30) D. F. Hunt and T. M. Harvey, Anal. Chem., 47, 1965 (1975). 31) D. F. Hunt and T. M. Harvey, Anal. Chem., 47, 2136 (1975). 32) M. Meot-Ner and F. H. Field, J. Am. Chem. Soc., 97, 2014 (1975). 33) 31, 1054 (1971). 34) G. A. Olah, Carbocations and Electrophilic Reactions, John Wiley, New York (1973). 35) M. Meot-Ner and F. H. Field, J. Chem. Phys., 64, 277 (1976). 36) M. Meot-Ner and F. H. Fioeld, J. Am. Chem. Soc., 100, 1356 (1978). 37) A. J. Cunninghum, J. D. Payzant, and P. Kebarle, J. Am. Chem. Soc., 94, 7627 (1972). 38) Y. K. Lau, S. Ikuta, and P. Kebarle, J. Am. Chem. Soc., 104, 1462 (1982). 39) A. G. Harrison, Interactions between Ions and Molecules, ed. by P. Ausloos, Plenum Press, New York (1975), p ) A. Good, Chem. Rev., 75, 561 (1975). 41) D. K. Bohme, D. B. Dunkin, F. C. Fehsenfeld, and E. E. Ferguson, J. Chem. Phys., 49, 5201 (1968). 42) M. Meot-Ner and F. H. Field, J. Am. Chem. Soc., 97, 5339 (1975). 43) W. N. Olmstead, M. Lev-On, D. M. Golden, and J. I. Brauman, J. Am. Chem. Soc., 99, 992 (1977). 44) P. V. Neilson, M. T. Bowers, M. Chau, W. R. Davidson, and D. H. Aue, J. Am. Chem. Soc., 100, 3649 (1978). 45) Y. Hatano, Electronic and Atomic Collisions, ed. by D. C. Lorents, W. E. Meyerhof, and J. R. Peterson, Elsevier Science Pub., Amsterdam (1986), p ) L. G. Christophorou, Atomic and Molecular Radiation Physics, John Wiley & Sons, London (1971), p ) B. M. Smirnov, Negative Ions, McGraw-Hill, New York (1982). 48) D. K. Bohme, G. I. Mackay, and J. D. Payzant, J. Am. Chem. Soc., 96, 4027 (1974). 49) J. D. Payzant, K. Tanaka, L. D. Betowsky, and D. K. Bohme, J. Am. Chem. Soc., 98, 894 (1976). 50) W. N. Olmstead and J. I. Brauman, J. Am. Chem. Soc., 99, 4219 (1977). 51) S. G. Lias and P. Ausloos, Ion Molecule Reactions, Am. Chem. Soc., Washington, D.C. (1975). 52) E. E. Ferguson, Atom. Data & Nucl. Data Tables, 12, 159 (1973). 53) L. W. Sieck and S. G. Lias, J. Phys. Chem. Ref. Data, 5, 1123 (1976). 54) D. L. Albritton, Atom. Data & Nucl. Data Tables, 22, 1 (1978). 55) Y. Ikezoe, S. Matsuoka, M. Takebe, and A. Viggiano, Gas Phase Ion Molecule Reaction Rate Constants through 1986, Maruzen, Tokyo (1987). 56) S. G. Lias, J. E. Bartmess, J. F. Liebman, J. L. Holmes, R. D. Levin, and G. Mallard, J. Phys. Chem. Ref. Data, 17, (1988), Supplement No ) P. Kebarle, Techniques for the Study of Ion Molecule Reactions Techniques of Chemistry Volume XX, ed. by J. M. Farrar and W. H. Saunders, Jr., John Wiley & Sons, New York (1988), Chap. V, p ) (1992), 7 p ) K. Hiraoka and S. Yamabe, Dynamics of Excited Molecules, ed. by K. Kuchitsu, Elsevier, Amsterdam (1994), 109

18 K. Hiraoka Chap. 11, p ) Y. K. Lau and P. Kebarle, J. Am. Chem. Soc., 98, 7452 (1976). 61) E. P. Hunter and S. G. Lias, J. Phys. Chem. Ref. Data, 27, 413 (1998). 62) R. Yamdagni and P. Kebarle, J. Am. Chem. Soc., 95, 4050 (1973). 63) K. Hiraoka, R. Yamdagni, and P. Kebarle, J. Am. Chem. Soc., 95, 6833 (1973). 64) T. B. McMahon and P. Kebarle, J. Am. Chem. Soc., 96, 5940 (1974). 65) T. B. McMahon and P. Kebarle, J. Am. Chem. Soc., 98, 3399 (1976). 66) T. B. McMahon and P. Kebarle, J. Am. Chem. Soc., 96, 4035 (1974). 67) T. B. McMahon and P. Kebarle, J. Am. Chem. Soc., 99, 2222 (1977). 68) J. B. Cumming and P. Kebarle, Can. J. Chem., 55, 3474 (1977). 69) R. Yamdagni and P. Kebarle, Can. J. Chem., 52, 861 (1974). 70) R. T. McIver, Jr. and J. T. Silvers, J. Am. Chem. Soc., 95, 8462 (1973). 71) R. T. McIver, Jr. and J. S. Miller, J. Am. Chem. Soc., 96, 4323 (1974). 72) E. M. Arnett, R. T. Small, R. T. McIver, Jr., and J. S. Miller, J. Am. Chem. Soc., 96, 5640 (1974). 73) A. L. C. Smit and F. H. Field, J. Am. Chem. Soc., 99, 6471 (1977). 74) D. F. Hunt and F. W. Crow, Anal. Chem., 50, 1781 (1978). 75) T. A. Roy, F. H. Field, Y. Y. Lin, and L. L. Smith, Anal. Chem., 51, 272 (1979). 76) H. P. Tannenbaum, J. D. Roberts, and R. C. Dougherty, Anal. Chem., 47, 49 (1975). 77) 53, 475 (2004). 78) 50, 234 (2007). 79) D. F. Hunt, G. C. Sta#ord, Jr., F. W. Crow, and J. W. Russel, Anal. Chem., 48, 49(1976). 80) G. H. Wannier, Bull. Syst. Tech. J., 32, 170 (1953). 81) M. McFarland, D. I. Albritton, F. C. Fehsenfeld, E. E. Ferguson, and A. L. Schmeltekopf, J. Chem. Phys., 59, 6620 (1973). Keywords: Ion/molecule reaction, Proton transfer reaction, Charge transfer reaction, Cluster ion, Negative ion 110