Mass Spectrometric Studies on Metal

CHEM.RES.CHI
NESE UNI
VERSI
TI
ES 2009,25(
2)
,228— 233
M ass
Spect
rom etri
c St
udi
es
on M et
a1
.
hexaf
lu0r0benzene Ani
oni
c
Compl
e
xe
s
(
M=Ag,
Au,Pd,Pt
,Pb and Bi
)
SUN Zha
ng ,SU
N Shu.
t
a
o ,LI
U Hong.
t
ao ,ZHU Qi
.
he ,GAO Zhe
n a
nd TANG Zi
.
c
hao
,
.
Be
ji
i
n
g Nat
i
o
nal
La
bo
r
at
or
yfo
r
Mo
l
e
c
ul
ar
Sc
i
e
n
ce
s
(
BNLMS
)
,St
at
e
Ke
y Labo
r
a
t
o
y r
o
fMo
l
e
c
u
l
ar
Re
ac
t
i
on
Dyna
mi
c
s
Ce
nt
e
r
o
fMo
l
e
c
ul
ar
Sci
e
nc
e
,
I
n
s
t
i
t
u
t
e
o
fCh
emi
s
t
r
y,Chi
ne
s
e
Ac
ad
emy o
fSc
i
e
nc
e
s
,
Be
o
'
i
n
g 1
00
08
0,
R.Chi
na
2.
St
at
e
Ke
y La
bor
at
o
r
y o
fMol
e
cu
l
ar
Re
ac
t
i
o
n
Dy
nami
c
s
,Da
l
i
a
n
I
ns
t
i
t
ut
e
o
fCh
e
mi
c
al
Ph
ys
i
c
s
,
Ch
i
n
e
s
e
Ac
a
de
my
o
fSc
i
e
nc
e
s
,Dal
i
an
1
1
60
23
,
R.Chi
na
Abs
t
r
ac
t
The
a
ni
o
ni
c
p
r
o
duc
t
s
f
r
om t
h
e
r
e
a
c
t
i
ons
be
t
we
e
n
me
t
a
l
(
M=Ag,Au,
Pd,
Pt
,
Pb
a
nd
Bi
)va
pou
r
p
r
o
duc
e
d by
l
ase
r abl
at
i
on and he
xaf
luor
obe
nzene s
eeded i
n car
ri
er
gas(
Ar
1
wer
e s
t
udi
ed by means
of a homemade
r
ef
lect
r
on t
i
me
-
o
f
-
li
f
g
ht
ma
s
s
s
p
ec
t
r
ome
t
r
y(
RTOF-
M S)
.
Exp
e
r
i
me
nt
al
r
e
s
ul
t
s
s
ho
w t
ha
t
t
he
do
mi
na
nt
pr
od
uc
t
s
we
r
e【
M C6
F6
]
一
compl
exes
f
or
t
he
r
eac
t
i
ons
of
Ag,Au,Pd a
nd Pt
wi
t
h C6
F6
,whi
l
e
t
he domi
na
nt
pr
oduc
t
s
wer
e【
M C6
F5
]
一compl
exes
f
0r
t
he
r
eact
i
ons
of Pb n d a
Bi
wi
t
h C6
F6
.The
or
f
mat
i
on mechani
s
ms
of t
he produc
t
s,i
ncl
udi
ng t
he
adsor
pt
i
on of
me-
t
al
cl
ust
er
ani
ons on he
xaf
luor
obenzene and t
he C— F cl
eavage i
nduced by met
al
cl
ust
e
r ani
ons
.wer
e di
scussed.
Keywords
Ti
me-
of
-
fi
ght
mass
s
pect
r
omet
er;M et
al
cl
us
t
er
;Ani
oni
c
compl
ex;React
i
on mecha
ni
s
m Art
i
cl
e ID 1005-
9040(
2009)
-
02-
228・
06
ha
r
dt
川 ca
r
r
i
e
d out
PES s
t
udi
e
s
of M2
Bz-
(
M=Pt
,Pd,
1
I
nt
roducti
on n d a
Pb)cl
us
t
e
r
a
ni
ons.Bowe
n gr
oup[
2
2
-2
4
】conduc
t
ed
The i
nteract
i
ons
of met
al
s
wi
t
h organi
c mol
e.
cul
es
are of f
undam ental
i
nteres
t
t
o chem i
cal
a
n d ma.
teri
al
s
ci
ences.Compounds
cons
i
st
i
ng of met
aI
cl
us—
ters
and mul
t
i
pl
e organi
c mol
ecul
es are preval
ent
i
n cl
assi
cal
orga
n omet
al
l
i
c and coor
di
nat
i
on chemi
st
ry,
PES s
udi
t
es
of
M (
Bz)
n
-
(
M=Ti
,Co,Fe,Ni
)cl
us
t
e
r
ani
ons.I
t
i
s known t
hat
benzene mol
ecul
es
a
r e prone to bei
ng di
ssoci
at
ed by m et
al
ani
oni
c cl
ust
ers.On t
he s
ur
face of ma
n y act
i
ve met
al
cl
ust
ers,for
exampl
e V【
5
1 Pt『
2
6]
Nb a
n d Rh[
2
7] benzene can be dehydro.
,
whi
ch coul
d provi
de useful
i
nfornlat
i
on for
f
ur
t
her
unders
ta
n di
ng som e i
mport
ant
heterogeneous
cat
al
yt
i
c pr
ocesses【
一钔
,
genmed or
di
ssoci
at
ed,wherei
n t
he hydrogen at
om s
are al
ways
observed t
o evol
ve as
H2
si
nce t
he reac—
. I
n recent
years. many exper
i
ment
al[
一1
6】 and t
heor
et
i
cal
[
1
7
—20
J
i
nvest
i
gati
ons on t
he i
nt
eract
i
ons
0f ti
ons a
r e t
her
m odynam i
cal
l
y prefer
red.Besi
des
,t
he s
tudy on t
he i
nt
eract
i
on of t
r
n si
a
t
i
on m et
al
a
n d phenyl
was
r
epor
ted.Xi
ng et
a1
.
1
Z8
1
repor
ted t
he genera
ti
on of met
al
cl
ust
ers
wi
t
h benzene i
n gas
phas
e have been r
ep0r
t
ed.Ar
ment
r
out
P
[
1
2
,
1
3
]s
t
udi
ed M Bz,
+
f
M = Ti
— Cu,Ag:Bz=be
nze
ne)vi
a c
ol
l
i
s
i
on-
i
nduc
ed di
s
.
【
M pheny1
]
一(
M=Mn,Cu)compl
exes
.The
phe
nyl
—
c
oi
na
ge
met
al
compl
exes[
Ag C6
H5
]
一a
nd[
AumC6
H5
]
一
soci
at
i
on exper
i
ment
s.Duncan group[
9
'
1
4】conduct
ed (
l一 3)
,a
nd
t
he
phenyl
—
l
ead me
t
a
l
compl
exes
phot
odi
s
s
oci
at
i
on
s
t
udi
es
on MBz (
M=Fe
,Mg,Ag [
Pb C6
H5
]
一
(
=1
— 5)we
r
e
s
t
udi
ed by vi
r
t
ue
of
PES
a
nd de
ns
i
t
y f
unct
i
onal
t
he
or
y(
DFT)
[
,
们.
a
nd Bi
)a
nd VBz
by me
ans
of
i
nf
r
red a
a
bs
or
pt
i
on spect
roscopy. Bowers
et
a1
.
[
们 i
nvest
i
gat
ed vana.
di
um/
benzene cat
i
oni
c cl
ust
ers by i
on mobi
li
t
y s
pec.
t
r
om et
y .Li
r
n et
a1
.
1
J
s
t
udi
ed t
he di
ssoci
ati
on of For
hexaf
luorobenzene.t
he subs
ti
t
t
l
t
i
on of luo.
f
r
i
ne f
or
hydrogen on t
he benzene ri
ng can bri
ng t
he
change of t
he bond st
rengt
h of i
oni
c丌compl
exes.The subs
t
i
t
ut
i
on of f
1
uori
ne for
hydrogen on t
he benzene M nBz a
n d CrBz by Four
ier
t
ransf
or
m.
i
on cycl
ot
ron r
es
ona
nc
e(
FT-
I
CR)
.Naka
j
i
ma
and Ka
ya
一 ,
pe
r
—
f
ormed mass
spect
rometr
y and phot
oi
oni
zat
i
on st
udi
es
on M-
Bz
c
l
us
t
er
s
a
nd t
he
i
r
cat
i
ons
(
M=Sc
- Cu)as
r
i
ng shoul
d set
st
r
onger
a
ni
oni
c bi
ndi
ng wi
t
h ben—
zene—
ri
ng f
luori
nati
on,but
t
hi
s
f
act
has
apparentl
y not
been veri
ied experi
f
ment
al
l
y.The st
udy of t
he reac.
ti
ons of met
al
s
wi
t
h C6
[
3
一。
has
not been extended
. wel
l
as t
he s
t
udi
es
of va
n adi
um.
.
r ena a
a
ni
oni
c com.
.
pl
e
xes
by phot
oe
l
ec
t
r
on s
pec
t
r
os
copy(
PES)
.Eber
-
Kaya gr
oup u s
t
udi
ed 【
(
C6
F6
)
l
_a
nd [
Au(
C6
F6
)
]
一
Co
r
r
e
s
po
ndi
ng
a
u
t
ho
r
.E—
mai
l
:g
a
oz
@i
c
c
a
s
.
a
c.
c
n
Recei
ved M ar
ch 26,2008;acce
pt
ed M ay 6,2008.
S
up
pose
d by
t
he
Na
t
i
ona
l
Na
t
u
r
a
l
Sc
i
e
nc
e
Fo
und
a
t
i
on
o
f
Ch
i
na
(
No.
20
433
08
0)
No.
2 SUN Zhang et
al
229 compl
exes by PES.Dunbar
et
a1
.
L
s
t
udi
ed t
he reac.
di
cul
ar
to t
h e mol
ecul
r bea
a
m a
n d wer
e ref
lect
ed t
o—
t
i
ons
of
Au十 a
nd Au。wi
t
h C6
F6
.However
,l
i
t
t
l
e
i
s
known about
t
he possi
bi
l
i
t
i
es
f
or a
ni
ons atached t
o wa
rd t
he
de
t
e
ct
oL mi
cr
oc
ha
nnel
pl
tes
a
(
MPC)
.The
r
es
ol
ut
i
on(
M/
AM)of
RTOF-
MS i
s
be
te
r
ha
t
n 2000,s
o face of benzene.The cl
ust
eri
ng of f
l
uori
de[
34
】a
n d i
t
i
s
easy t
o assi
gn t
he product
s by t
he m ass
spect
r
um.
chl
ori
de[
,
。
] i
0ns wi
t
h s
om e ar
omati
cs i
ncl
udi
ng .
some par
t
i
al
l
y f
luor
i
nat
ed benzenes
,has
been report
ed,
and i
t
i
s
consi
dered that
t
hese ar
e hydr
ogen.
bound 3 Resul
t
s and Di
scussi
on The ani
oni
c pr
oducts
from the react
i
ons
of al
l
t
he compl
exes
not
t
o be ver
y rel
eva
nt
t
o t
h e 7
z
-
.
bound st
udi
ed met
al
sampl
es wi
t
h C6
F6
were genera
t ed under
compl
exes
of m et
al
ni
a
ons.
the si
mi
l
r experi
a
ment
a1
condi
t
i
ons as
s
hown above.
W e carri
ed out
a mass spect
romet
ri
c i
nvest
i
gat
i
on The
wa
ve
l
engt
h of
t
he
l
as
e
r
(
1
064 nm or
532
m )us
u
ed of t
he r
eact
i
ons
bet
ween hexaf
luor
obenzene seeded i
n o r t
f
he abl
at
i
on had l
i
t
tl
e efect
on t
h e product
di
s仃i
—
c
ar
r
i
e
r
gas
a
nd met
al
(
M Ag,Au,Pd,Pt
,Pb a
nd Bi
)
but
i
on.The seedi
ng of hexaf
lurobenzene i
n t
he cari
er vapour
produced by l
aser abl
ti
a
on.El
ect
roni
cal
l
y,Ag gas
(
Ar
)ca
n pr
o
mot
e
t
he
gr
owt
h of
me
t
al
c
l
us
t
e
r
s
n d a
Au have a fi
l
l
ed d shel
1
combi
ned wi
t
h a 5s a
n d whose underl
yi
ng mecha
ni
sm has
been report
ed i
n t
he 6s val
ence shel
1
.respect
i
vel
y.Pd a
n d Pt
have a 4d ” publ
i
shed paper[
2
8
] The r
eact
i
ons
bet
w een m et
al
s
and and 5d 6s
val
ence shel
1
.respect
i
vel
y.And Pb a
n d Bi
orga
ni
c mol
ecul
es
ca
n efect
i
vel
y rel
ax t
he i
nt
em a1
have a 6s n d 6s a
.
val
ence s
hel
l
,res
pect
i
vel
y.
ener
gy of t
he pl
asma generat
ed by l
aser
abl
at
i
on on Because of t
hei
r
di
ferent
val
ence el
ect
rons.仇 e do.
met
aI
sam pl
e.whi
ch i
s
adva
nt
ageous t
o the f
o rma
ti
on mi
nant
pr
oduct
s
of t
he react
i
ons
of t
hese metal
s wi
t
h of l
r ger
a
si
ze cl
ust
er
speci
es i
n t
he st
ar
t
i
ng par
t
of t
he C6F6
are di
f
ferent
f
rom each ot
her.The react
i
on me.
reacti
on channe1
.Thi
s phenomenon has
al
ready been Observed i
n 0ur Dr
evi
ous
experi
m ents[
28
,
3
8,
3
9
1
chani
sms,i
ncl
udi
ng t
he adsorpt
i
on of metal
cl
ust
er
. ani
ons
on hexafl
uOr
Obenzene and t
he sel
ecti
ve C——F The experi
ment
s
show t
ha
t t
he l
ower
part
i
al
cl
eavage of t
he hexanuOrObenzene i
nduced by met
al
pr
es
s
ur
e of
hexaf
luor
obe
nze
ne
(
<0.
1% of
he
t
mi
xed cl
ust
er n i
a
ons
were pr
oposed.
gas
)f
avor
s
t
he
f
or
m at
i
on of
ni
a
oni
c c
l
us
t
er
s
.Ot
he
r
.
wi
s
e,som e byproduct
s,such as
mul
t
i
pl
e hexaf
luor
o—
2 Exper
i
m ent
al
Met
hods benze
ne
compl
e
xes 【
(
C6
F6
)
】
一
,woul
d a
ppe
r.The
a
The apparat
us
used i
n t
he experi
m ent
s
mai
nl
y pr
esent
at
i
on of t
he domi
nant
a
ni
oni
c products
i
dent
i
—
consi
s
ted of a homem ade ref
lect
r
on t
i
me—of-
li
f
ght
ned by t
he m ass spect
u m i
r
s
not
sensi
t
i
ve t
o t
he l
aser ma
ss
s
pect
r
ome
t
er
(
RTOF—
M S1
wi
h a l
t
a
se
r
s
ys
t
e
m.
i
ntensi
t
y a
n d t
he pressure of car
ri
er
gas
used i
n t
h e The det
ai
l
of the aDpa
r at
us has
been publ
i
shed el
se.
experi
ment
s.whi
ch wi
l
l
be di
scussed i
n t
he f
ol
l
owi
ng whereL
/
1 and onl
y an out
l
i
ne i
s
gi
ven bel
ow.
part
s.
,
The
me
t
a
l
(
M)di
s
k t
a
r
ge
t
s
(
pur
i
t
y>99.
9%)i
n t
he
sour
ce chamber
of I
OF.
M S were abl
ted by a a
3.
1
Product
Anal
ysi
s by M ass Spectrom et
ry pul
s
e
d l
a
s
er
bea
m(1
064
nm or
532 nm Nd:
YAG l
as
e
L Fi
gs
.
1
—3
s
how t
he
ypi
t
c
al
ma
s
s
s
pec
t
r
a
of
a
ni
o—
5 Hz ~1
0 mJ/
puls
e1
a
n d t
he t
argets
wer
e r
ot
at
ed du.
ni
c product
s f
rom t
he r
eact
i
ons
bet
ween di
ferent
va.
ri
ng t
he exper
i
ment
s.The l
aser
-i
nduced pl
asma was
por
i
ze
d me
t
al
s
peci
es
(
M=Ag,Au,Pd,Pt
,Pb and Bi
)
car
ri
ed by t
he m ol
ecul
ar
bea
m gener
at
ed from a n d hexaf
a
l
uorobenzene mol
ecul
es,r
espect
i
vel
y.The pul
sed val
ve t a
a backi
ng pressure of about
400 kPa of hi
gh resol
ut
i
on Of I
oF.
M S al
l
ows t
h e exact
i
dent
i
.
rgon(
a
pur
i
t
y 99.
99%)
,i
n whi
c
h he
xa
f
1
uor
obenze
ne
icati
f
on of t
he i
sot
opi
c di
st
r
i
buti
on i
n the mass
regi
on was seeded.The vol
um e r
at
i
o of hexaf
luqrobenzene i
n of these s
pect
ra.Al
l
t
he mass spect
ra were ca
r eful
l
y t
he mi
xed gas
was not
more t
ha
n 0.1% . The cal
i
bra
ted accordi
ng to t
he m ass number
of pure m et
a1
M m-
hexaf1
uorobenzene a
ni
ons
generat
ed f
rom t
h e cl
us
ters.
r
eact
i
ons
of metals
wi
t
h hexaf
luorobenzene were en.
h e a
n
Fi
gs
.
1(
A)a
nd (
B)
show t
i
oni
c product
s
t
r
ai
ned by t
h e carr
i
er
gas
t
ha
t under
went a l
ow pre t
h hexafl
uOrObenzene a
n d f
rom t
he r
eact
i
ons of Ag wi
s
s
ur
e
(
10 Pa、i
n t
he
s
our
c
e c
ha
m ber
.Af
t
e
r
pa
s
si
ng a
Au wi
t
}
l
hexaf
luorobenzene。Fr
om Fi
g.
1.we ca
n i
den—
s
ki
mm er,al
l
t
he pr
oduct
s
entered i
nt
o t
he accel
erat
i
on t
i
f
y four di
ferent
seri
es of a
ni
oni
c com pl
exes:
a
r
ea i
n t
he
s
pec
ros
t
c
opi
c
cha
m be
r
(
10-
4 Pa)
.The
ani
o.
[
[
V
[
mC6
F4
】
一
,I
M C6
F5
]
一
,[
MmC6
F6
]
一a
nd [
M C6
F7
]
一
(
M=Ag a
nd
Au)
,a
n d[
M C6
F6
】一compl
e
xes
ar
e do—
ni
c cl
ust
ers were accel
era
t ed i
n t
h e di
rect
i
on per
p en.
230 CHEM .RES.CHI
NESE UNI
VERSI
TI
ES Vb1
.
25 mi
nant
ani
oni
c product
s.The i
nt
ensi
ti
es of t
hese com-
r
eact
i
on of Ag and benzene,
ma
n y f
ragment
s
pl
exes i
n m ass s
pect
r
um decreas
e wi
t
h the i
ncrease of [
AgC Hk
]
一(
1
—1
2,
1
— 5)a
re
pr
es
e
nt
ed bas
ed
on number
m.These res
ul
ts
are i
n agreement
wi
t
h t
he t
he mass spect
u m r
whose i
nt
ensi
t
i
es
a
r e t
he sam e
as
publ
i
shed resul
t
s【
jl
1
. The di
ier
f
ence bet
ween t
he t
he
ones
of
he
t
domi
na
nt
pr
oduc
t
s[
Ag C6
H5
]
一
(
1
,
compl
exes contai
ni
ng Ag or
Au i
s t
hat
t
he number m 2 .Thi
s fact
s
hows h at
t
t
he benzene r
i
ng i
s
broken up ofAg cal
l
reach 2 and t
he number m OfAu Cal
l
reach 4.
by Ag cl
ust
er
ani
on.W l
e ca
n see t
ha
t i
n Fi
g.
1,t
he i
n-
Howeve ̄ f
or t
he react
i
ons
of Ag and Au wi
t
h benzene,
t
ens
i
t
i
es
of t
he
pea
ks
at
t
r
i
but
e
d t
o[
Ag2
C F 一
(
4—7,
t
he
domi
na
nt
pr
oduc
t
s
ar
e【
M C6
H5
]
一
(
M=Ag n d a
Au,
k=
-4.
51
ar
e very weak whi
ch shows
t
ha
t t
he s
ubst
i
t
u—
l一 31
dehydrogenat
ed compl
exesL
J
.and t
her
e a
re t
i
on of luori
f
ne f
o r hydrogen on t
h e benzene ri
ng f
a-
=
no【
M C6
H4
]
一
,【
M C6
H6
]
一a
n d I
S C6
H7
]
一c
ompl
e
xes
vors
t
he s
t
abi
l
i
zat
i
on of t
he aroma
ti
c ri
ng.
accordi
ng t
o t
he mass
spect
u m .Especi
r
al
l
y f
o r t
he 70 t
(
Fl
i
ght
)
/
 ̄
s
90 l10 l30 150 l70 190 t
(
Fl
i
ght
)
/
gs
Fi
g
.
1
Ty
pi
c
a
l
mas
s
s
pe
c
t
r
a
o
f
a
ni
o
ni
c
pr
o
duc
t
s
o
bt
ai
ne
d
f
r
om r
e
ac
t
i
on
s
be
t
we
e
n
v
apo
r
i
ze
d
Ag
(
A)
,
Au(
B)
and hexaf
luorobenzene,re
spect
i
vel
y The
i
ns
e
t
i
n(
A)s
hows
t
he
e
nl
a
r
g
e
d pa
r
t
of
he
t
s
pe
c
t
r
um.(
A)▲ Ag
mC6
F4
一
(
=1
,
2
)
;_Agn
,
C6
Fs
-
(
m=1
,
2
)
;・AgmC6
F6
一
(
=1
,
2)
;
A C6
F7
(
=1
,
2)
.(
B)▲ AumC6
F4
一
(
=1
- 4)
;-AumC6
F5
一
(
=1
-4
)
;・AumC6
F6
-
(
m=1
-4
)
;V
Au
mC6
F7(
m=1
- 4)
・
rA .
q l Fi
gs
.
2(
A)a
nd (
B)s
how t
he
a
ni
oni
c pr
oduc
t
s
Howeve
r
,Li
u et
a1
.
r
epor
t
e
d t
hat
t
he pr
oduc
t
s
rom t
f
he reacti
ons of Pd wi
t
h hexaf
luor
obenzene and r om the r
f
eact
i
on bet
ween Pt
and benzene a
r e Pt
wi
h hexaf
t
l
uor
obe
nz
ene,r
es
pe
ct
i
vel
y I
n Fi
g.
2,
t
hr
e
e
s
e
r
i
es
of 【
M C6
F5
]
一
=l
一 3)
,
v
I
C6
F6
]
一
(
=1
— 4) a
nd [
M C6
F7
】
一
(
=1
— 4)
(
M:
=
Pd a
nd Pt
)
compl
exes
a
r
e
i
de
nt
i
ied,a
f
n d t
he 【
M C6
F6
]
一com-
【
Pt
C6
H4
]
一
, [
Pt
C1
2
Hk
]
一 a
nd [
Pt
mC6
H4
…(
C6
H6
)
】
一
(
m 1—4)compl
e
xes
a
nd
t
he
r
e
a
r
e
no [
Pt
mC6
Hs
]
一
,
[
Pt
mC6
H6
]
-a
n d[
Pt
mC6
H7
]
一compl
e
xes
pr
es
e
nt
.Eber
—
ha
r
dt
et
a1
.
r
epor
t
e
d t
he
chemi
s
or
pt
i
on of
be
nz
ene
pl
exes
are dom i
na
nt
ani
oni
c product
s.The i
nt
ensi
t
i
es
on Pd and Pt
ani
ons,but
the resol
uti
on of t
hei
r mass
of pea
ks
assi
gned to t
hese compl
exes i
n t
he mass
spect
ra was too poor t
o r
esol
ve t
he number
of hydr
o-
s
pect
r
a decrease wi
t
h t
he i
ncrease of number
m .
gen at
om s
i
n t
he products.
t
(
Fl
i
g
ht
)
/
 ̄
t
(
Fl
i
ght
)
/
 ̄s
Fi
g.
2 Typi
cal
mas
s
spec
t
ra of
ani
oni
c
product
s
obtai
ned rom f
re
act
i
ons
bet
ween vapor
i
zed Pd(
A)
,Pt
(
B)
and he
xaf
luorobenzene,res
pect
i
vel
y The
i
ns
e
t
s
i
n
t
he
s
pe
ct
r
a s
how he
t
e
nl
ar
ge
d p
ar
t
oft
he
s
pe
c
t
r
a
,r
e
s
pe
c
t
i
ve
l
y.(
A)_PdmC6
F5
一
(
m l
一3)
;・Pd
mC6
F6(
m 1
—3)
;
V Pd,
”
C6
F7(
1—4)
.
(
B)一 Pt
m
C6
Fs
-
(
m=l
-3)
;・P C6
一
(
1
—4)
;T
C6
F7
一
(
m=1
— 3)
.
Fi
gs
.
3(
A)and(
B)s
how t
ypi
c
al
mas
s
s
pec
t
r
a of
t
he ani
oni
c products
f
rom t
he react
i
ons
of Pb wi
h t
(
m=l
一 5)
,[
Pb C6
F5
]
一a
nd[
Pb C6
F6
]
一
(
m 1—6)a
re
hexaf
luorobenzene and Bi
wi
t
h hexanuorObenzene.
i
dent
i
ied,and [
f
ebmC6
F5
]
一def
l
uor
i
na
t
e
d c
ompl
exes
ar
e domi
nant
ni
a
oni
c
pr
oduct
s.I
n Fi
g.
3(
B)
,t
he
f
ive I
n Fi
g_
3(
A)
,t
he
f
our
s
er
i
e
s
of[
Pb 】
一
,[
Pbm"
C6
F4
]
一
s
er
i
e
s
of [
Bi
】
一
1
— 5)
,[
Bi
C6
F3
]
一(
m 2— 5)
,
No.
2 SUN Zhang etal
[
Bi
C6
F4
]
一
(
1
— 5)
, Di
C6
F5
]
一 (
m l一5)
a
nd =
231
l
一1
6,
l
一 5) f
r
agme
nt
s
a
n d met
al
cl
us
t
er
s
【
Bi
C6
F6
]
一
1
— 4)a
r
e
i
de
nt
i
ied,and 【
f
Bi
C6
F5
]
一
[
Pb 】
一
(
=1— 1
1)pr
es
e
nt
on t
he
bas
i
s
of
t
he
mass
defl
uori
nat
ed compl
exes
are dom i
nant
ani
oni
c pro—
spect
rum a
n d they al
l
have i
ntense peaks.But
f
or t
he ducts.These experi
ment
al
res
ul
t
s are si
mi
l
ar
to t
hose react
i
ons
of Pb or
Bi
wi
t
h C6F6,t
he i
nt
ensi
t
i
es of of t
he r
eact
i
on bet
ween Pb and benzene,i
n whi
ch t
he domi
na
nt
pr
oduc
t
s
a
r
e[
Pb C6
H5
]
一
l
一 5)de
hy-
drogenat
ed compl
exest
1
5] Nevert
hel
ess t
he di
ff
e—
[
M C 一
=1
— 4,,
2
=4— 6,
1—3)f
ra
gment
s
i
n t
he mass
spect
rum a
r e very wea
k ,whi
ch s
hows t
h at
t
he subst
i
t
uti
on of luori
f
ne f
or
hydrogen on t
h e ben-
.
rence i
s so promi
nent
t
hat
for t
he r
eacti
on between Pb and C6
H6
,t
he
r
e
a
r
e
ma
ny 【
Pb C Hk
]
一
(
1—2,
zene ri
ng favors
t
he st
abi
l
i
zat
i
on of t
h e a
r om at
i
c ri
ng.
t
(
Fl
i
ght
)
/
 ̄ t
(
Fl
i
ght
)
/
 ̄ Fi
g.
3 Typi
cal
m ass
spect
ra of
ani
oni
c
products
o
bt
a
i
ne
d
f
r
om r
ea
c
t
i
ons
be
t
we
e
n
vapor
i
z
e
d Pb(
A)
,
Bi
(
B)
and hexaf
luorobenzene,respecti
vel
y The
i
ns
et
i
n(
A)s
ho
ws
t
he
e
nl
ar
ge
d
pa
r
t
of
t
he
s
pe
c
t
r
u
m.(
A)・Pbm-
(
,
,
F
]
:
1
——6)
;▲ Pb
mC6
F4
_
(
=1
—6)
;・PbⅢC6
Fs
-
(
m=1
— 6)
;V
Pb
C6
F6
一
(
=l
一6)(
B)・Bi
?
H
-
(
=1
— 5)
;◆Bi
C6
F3
一
(
,
,
2
=2—5)
;▲ Bi
卅C6
F4(
=1
— 5)
;_Bi
mC6
F5(
=1
~5
)
;V Bi
卅C6
F6
_
(
=1
— 5)
.
From t
he experi
ment
al
resul
ts
shown above,we met
al
s
or
coi
nage m etal
s
wi
t
h benzene have been can get
t
he concl
usi
on t
hat
t
he di
st
ri
but
i
ons
of m e di
scussed i
n previ
ous publ
i
cat
i
on【
1
5
,
28,
4
6】 A ccor—
products
generated from t
he react
i
ons between me—
di
ngl
y t
he for
m ati
on mechani
s
ms
of t
he ani
oni
c t
a
l
s
(
M=Ag,Au,Pd,Pt
,Pb a
nd Bi
)a
nd
he
xa
f
l
uor
o-
pr
oduc
t
s【
M C6
Fn
】
一
(
=l一 6,
5— 7)ar
e pr
opos
ed
benzene are di
fferent
f
rom each ot
her.a
n d t
he do.
as
Schem e 1.
mi
nant product
s from t
he reacti
ons bet
ween m e—
. Ar [
Mm]
一
十(
C6
F6
)
——}
【
M …(
C6
F6
)
]— —}
【
M C6
F6
]
一
(
1
)
A r t
a
l
s
(
M=Ag,Au,Pd a
nd Pt
)and he
xaf
luor
obenz
ene
[
M r+(
c6
F6
)
——}
【
M …(
C6
F6
)
]
一— —}
[
Mm]
+[
C6
F6
]
一
(
2)
are di
ff
erent
f
rom t
hose generated f
rom t
he react
i
ons
【
M ]
_
+(
c6
F6
)
—— 【
M …(
c6
F6
)
r_
_
【
M C6
F5
】
一
+【
c6
F7
】
(
3)
be
t
ween me
t
al
s
(
M=Pb and Bi
)a
nd
he
xaf
luor
oben—
【
M ]
_
+(
c6
F6
)
—_
÷
[
M …(
c6
F6
)
r 兰 !
【
M C6
F5
1
+[
c6
F7
】
一
(
3
)
zene.Compar
ed w i
t
h t
he react
i
ons
of m etal
s
wi
t
h 【
M 】
(
c6
F6
)
—— [
M …(
c6
F6
)
r !
【
M C6
F7
】
_
+【
c6
F5
】
(
4)
be
nz
ene
,t
he i
nt
e
ns
i
t
i
es
of peaks
of
t
he【
M C F —
【
Mm]
_
+(
c6
F6
)
— }
【
M …(
c6
F6
)
r 【
M卅C6
F7
】
一
+[
c6
F5
r (
4 )
[
M r (
c6
F6
)
——}
【
M …(
c6
F6
)
r 【
M C6
F5
]
-
+MF
(
5)
r agm ent
f
pr
oduct
s
pr
esent
ed i
n t
he mass spect
rum are very weak.Thi
s i
m pl
i
es
t
hat
t
he s
ubst
i
t
ut
i
on of fl
uori
ne f
o r hydrogen on t
he benzene ri
ng favors t
he st
abi
li
zat
i
on of t
he aromat
i
c ri
ng.I
t
i
s known t
hat
t
he bond ener
gy of
phenyl
— F i
s
54
kJ/
mol
hi
ghe
r
han t
t
hat
of phenyl
- H[
41
] Some publ
i
cat
i
ons[
一 】show .
t
hat
t
he C— H bond act
i
vat
i
on reacti
on by t
ransi
ti
on m et
al
s i
s
t
hermodynam i
cal
l
y f
avor
abl
e and has
l
ess energY barri
er than t
he C— F bond act
i
vat
i
on reacti
on.
So i
f the m etal
cl
uster
a
ni
ons have not
ener
gy enough t
hey can not dest
roy the aromat
i
c ri
ng of hexaf
luo—
robenzene.
3.
2 Form at
ion M echani
sm Scheme 1
Possi
bl
e
f
ormat
i
on mechani
sms
of【
M mC6
F^r (
J
,
l
=l一 6,,
l
=5— 7)compl
exes
From Fi
gs.1— 3.we can al
so s
ee ma
n y ani
oni
c ragme
f
nt
pr
oduct
s[
C6
F5
]
一
,[
C6
F6
]
一a
nd [
C6
F7
]
一
.
However,t
he experi
ment
s di
d not
show t
hat
t
he ca—
t
i
ons[
C6
F5
]
,[
C6
F6
]
and [
C6
F7
]
ar
e
t
ot
al
l
y ob—
served i
n t
he same experi
ment.Thi
s f
act
i
mpl
i
es t
hat
t
he generat
i
on of these a
ni
oni
c f
r agment
s r
esul
t
s
f
rom t
he generati
on of m etal
ani
oni
c cl
ust
er
s.Thi
s
si
t
uat
i
on i
s si
mi
l
ar
t
o t
hat
of t
he r
eact
i
ons
bet
ween m et
al
s and benzene.Xi
ng f口,
.
[
28
】r
eport
ed t
hat
t
he C— H cl
eavage of benzene was caused by t
he metal
cl
ust
er
ani
ons.
The f
or
m ati
on mechani
sm s
of t
he product
s For【
MmC6
F6
]
一pr
oduc
t
s,t
he mos
t
pos
s
i
bl
e
me—
cha
ni
s
m i
s
t
he pa
hwa
t
y(1
)i
n Sc
he
me
1.I
n t
he
cl
us
—
[
M C6
H5
]
一gener
a
t
ed rom f
t
he
r
e
ac
t
i
ons
of t
r
ns
a
i
t
i
on t
er
i
on source,t
he met
al
speci
es
di
r
ect
l
y m erge i
nt
o 232
CHEM .RES.CHI
NESE UNI
VERSI
TI
ES Vl
01
.
25
the hexaf
luorobenzene/
argon reagent. The excess
As f
o r t
he bondi
ng pat
ter
n of t
hese domi
na
nt
energy,whi
ch i
s l
ef wi
t
hi
n m etal
cl
ust
er
s due t
o l
a—
product
s,we pr
opose t
he fol
l
owi
ng bondi
ng pat
t
er
n.
ser abl
ati
on or
t
he col
l
i
si
on process
wi
t
h hexaf
luo—
For
t
he [
MmC6
F6
]
一compl
e
xes
,t
he
mos
t
pos
si
bl
e
robenzene,can exci
t
e t
he react
i
on sys
tem t
o f
orm bondi
ng pat
t
er
n i
s
t
he i
nt
eracti
on of m etal
cl
ust
ers [
Mm…(
C6
H6
)
]
一i
nt
e
r
medi
a
t
e.
And t
hi
s
i
nt
er
medi
a
t
e
i
s
wi
t
h :
r
-or
bi
t
al
of C6F61
1
7,
4
7,
48
]
col
l
i
ded by Ar
at
om s
subsequentl
y, whi
ch t
akes
compl
exes,the mos
t
possi
bl
e one i
s t
hat
t
he C6F a
wa
y t
he
e
xces
s
ener
gy t
o f
or
m[
MmC6
F6
]
一pr
oduc
t
s,
group bonds
on t
he met
al
cl
us
t
er vi
a t
he met
al
-
or
breaks
down the weak “bond” of t
he car
bOn盯bondI
[
2
9,
30
,
4
6]
[
M …(
C6
H6
)
]
一i
nt
er
medi
at
e
t
o f
or
m[
C6
F6
]
一,s
hown i
n t
he
pa
t
hwa
y(
2)i
n Sc
he
me
1.
.
For
t
he [
MmC6
F5
1
一
. 4 ConcI
usi
ons For【
MmC6
F5
]
一a
nd [
M C6
F7
]
一pr
oduc
t
s
,t
he
I
n summ ary,the react
i
ons
bet
ween t
he metal
mos
t
pos
si
bl
e
me
cha
ni
s
ms
ar
e
t
he
pat
hwa
ys(
3)and s
peci
es
(
M Ag,Au,Pd,Pt
,Pb and Bi
)va
por
i
ze
d by (
4)i
n Scheme
1.Whe
n t
he
C—F bond i
s
br
oken l
aser abl
at
i
on and hexanuorobenzene seeded i
n ca
r.
down due
t
o t
he
col
l
i
s
i
ons
bet
wee
n[
Mm…(
C6
H6
)
]
一
a
nd[
C6
F6
]
,t
he
F at
om c
an bond wi
t
h[
C6
F6
】t
o f
or
m ri
er
gas have been s
tudi
ed by a ref
l
ect
r
on t
i
me—
【
C6
F7
]a
nd[
MmC6
F5
]
一c
ompl
e
xe
s
,or
F at
om bonds
gai
ned f
rom t
he r
eacti
ons bet
ween m et
al
s
d C6
F6
wi
t
h[
M C6
F6
】t
o f
or
m 【
MmC6
F7
]
一and 【
C6
F5
]
.The
are metal
-
hexanuOrObenzene compl
exes.whi
ch are el
ec
t
r
on can al
s
o equal
l
y bond wi
t
h [
C6
F5
] and di
fferent
f
rom t
he ones of t
he r
eacti
ons bet
ween [
C6
F7
]
,s
o t
he
pat
hway(
3
)and pa
t
hwa
y(
4 )a
r
e
bot
h metal
s and benzene[
28,
29,
40] The dOmi
nant
ani
Oni
c possi
bl
e. The probabil
i
t
y of t
he col
l
i
si
on bet
ween products
observed i
n Ag,Au,Pd and Pt
syst
ems
are 【
M …(
C6
H6
)
]
一 and [
C6
F6
】i
s
compa
r
at
i
vel
y s
mal
l
[
M C6
F6
]
一compl
exes
,a
nd t
he
ones
obs
er
ved
i
n Pb of-
li
f
ght
mass s
pect
romet
r
y. The
ani
oni
c products
.
due
t
o
t
he
s
mal
l
vol
ume
r
a
t
i
o
of[
C6
F6
]i
n t
he
ca
r
r
i
er
a
nd Bi
s
ys
t
e
ms
ar
e[
M C6
F5
]
一def
luor
i
na
t
e
d com—
gas,s
o
t
he
i
nt
ens
i
t
i
es
of
t
he pe
aks
of【
M C6
F5
]
一and pl
exes.The r
eact
i
on mechani
sms of t
hese products
【
MmC6
F7
]i
n mas
s
s
pec
t
r
um a
r
e
weak.I
n or
der
t
o are proposed,i
ncl
udi
ng t
he adsorpti
on of m et
al
cl
us-
pass
t
hr
ough the above react
i
on pat
hways, i
t
i
s ter ani
ons
on hexaf
luOrObenzene and t
he C——F cl
ea.
needed t
o over
come t
he hi
gher ener
gy barr
i
er
of vage of hexaf
luorobenzene i
nduced by m et
al
cl
ust
ers
t
r
a
ns
i
t
i
on s
t
at
es
(
TS)
t
of
t
he
Dr
oduc
t
s
.The
exces
.
i
n t
he gas phase.To conf
ir
m the geom et
ri
c s
tr
uct
ures
si
ve energy wi
t
hi
n hot
metal
cl
ust
er
s provi
ded by of t
hese compl
exes,t
he st
udy by combi
nati
on of t
he l
aser
vapor
i
zat
i
on is
com pet
ent
t
o overcome t
he phot
oel
ect
ron s
pect
roscopy and ab i
ni
t
i
o cal
cul
at
i
ons
ener
gy bar
ri
er.
f
or
t
he[
M C6
F6
]
一and[
MmC6
F5
]
一compl
exes
i
s
now For heavy met
al
s
Pb and Bi
,t
he domi
nant
pr
oduct
s
a
r
e
【
M C6
F5
]
一
compl
e
xes
,
a
nd t
he
[
MmC6
F7
]
一pr
oduct
s
di
s
appear
acc
or
di
ng t
o t
he
ma
s
s
spect
rum .
So t
he f
or
m a
ti
on m echani
sm of 【
MmC6
F5
]
一
(
M=Pb and Bi)i
s
di
f
f
e
r
ent
f
r
om t
ha
t
of [
MmC6
F5
]
一
(
M=Ag,Au,Pd a
nd
Pt
)
.The
mos
t
poss
i
bl
e
f
or
ma
t
i
on mechani
sm of[
MmC6
Fs
]
一i
s
pa
t
hway(
5)
i
n Schem e 1.The heavy met
al
s
Pb and Bi
abl
at
ed by l
as
er
a
r
e
pr
one
t
o
f
or
m cl
us
t
er
s[
Mm]
一
,whi
ch a
r
e
i
denti
ied i
f
n mass s
pect
rum .W hen t
he i
ntermedi
t e a
[
Mm…(
C6
H6
)
]
一 col
l
i
des
wi
t
h me
t
al
M or[
M 】
,a
n i
nset
react
i
on wi
t
h t
he cl
eavage of C— F bond t
akes
pl
a
ce,a
nd t
he pr
oduct[
MmC6
F5
]
~yi
el
ds
wi
t
h r
el
ea
—
si
ng F at
om .The F a
t om can bond wi
t
h M t
o form M F.Thi
s
cl
eavage of C— F bond i
s
not
easy t
o t
k e a
pl
ace due t
o t
he hi
gher
bar
ri
er
of t
ransi
ti
on s
t
a
t
e(
TS)
,a
nd
t
he
e
xces
s
i
ve
ener
gy wi
t
hi
n hot
m et
al
cl
ust
er
s provi
ded by l
aser
vapori
zat
i
on pro—
mot
es
t
he
f
or
mat
i
on of[
MmC6
F5
]
一compl
e
xes
.
under
way.
References [1
] La
nd
man
U.
,Lue
dt
ke
W.D.
,Bur
nham N.A.
,e
t
al,Sc
i
e
nc
e,1
990,
24
8(
495
4)
,45
4 [
2
】 Xu Z.
,Xi
a
o F
S.
,Pur
nel
l
S.K.
,e
t
al,Nat
ur
e
,199
4,37
2(
65
04)
,
346 [
3] Cl
e
vel
a
nd C.L.
,Land
man
U.
,Sch
aa
f T.G.
,
et
a1
.
,Phy
s.Rev
Le
t
t
19
97,7
9(
1
0)
,18
73
[
4] Ha
kki
nen
H.
,Ba
ne
r
t
t
R.
N.
,Sc
her
bak
ov A.
G.
,e
t
al
,
eh
ys
Che
m B,
2000,10
4(
39
)
,906
3
[
5】 Hos
hi
no K.
,Kur
i
ka
wa
T.
,Ta
keda
H.
,e
t
a1
.
,
Ph
ys
Che
m ,199
5,
99
(1
O)
,3053
【
6】 Kur
i
ka
wa
T.
,Hi
r
a
no M.
,Ta
ked
a
H.
,et
a1
.
,
Ph
ys
Chem,1
995,
99(
44)
,1
6248
[
7] Kur
i
ka
wa
T.
,Ta
ke
da H_
,Hi
r
a
no
M.
,e
t
a1
.
,Or
ga
nome
t
al
l
i
c
s
,199
9,
18
(
8)
,1
430
【8
] Ra
yane
D.
,Al
l
o
uche
A R.
,Ant
oi
ne
R.
,e
t
al,Ch
em.P .Le
t
t
.
,
200
3,
37
5(
5
/
6
)
,50
6 [
9] Va
n He
 ̄n
s
ber
ge
n D.
,Von He
l
den
G.
,Mei
j
e
r
G.
,et
al,
Am Che
m Soc
.
,20
02,1
24(
8)
,1
562
[
1
0】 Wei
s
P.
,Ke
mpe
r
P.R.
,Bowe
r
s
M .T.
,
en
ys
Che
m.A,1
997
,
No.
2 lol
(
4
4)
,8207
SUN Zhang etal
.
233
lO9(
51
)
,11
742
【
l
1】 Li
n C.Y.
,Che
n Q.
,Che
n H.P.
,e
t
a
1
.
,
eh
ys
.Chem.A,1997,
101
(
3
4)
,60
23
【
30】 Li
u H.T.
,Xi
ng X.P.
,Su
n S.T.
,e
t
a1
.
,
Ph
ys
.Chem.A,2006,
110
(
28)
,8
688
【
1
2】 Mey
er
F.
,Kha
n F.A.
,Ar
me
nt
t
ou
t
P.B.
,
Am:Chem.Soc
.
,1995
,
JJ
7
(
3
8)
,97
40 【
3l】 Naka
j
i
ma
A.
,Ta
guwa T.
,Ho
s
hi
no K.
,e
t
a1
.
,Chem.Ph
ys.Le
t
t
.
,
19
93,21
1
)
’2
2 【
1
3】 Che
n Y.M.
,Ar
me
nt
r
ou
t
P.B.
,Che
m.
Ph
ys.
Le
t
t
.
,1
993,2JD(
1
—3
)
,
【
32
】 HoY.P.
,Dunba
rR.C.
,l
nt
.
Mas
s
s
pec
t
r
om.
,19
99,182
/
183,1
75
【
33
】 Ca
ra
i
ma
n D.
,Koya
nag
i
G.K.
,Bohme
D.K.
,
eh
ys
.Che
m.A,
123 ●
【
1
4】 Wi
l
l
e
yK.F.
,YehC.S.
,Robbi
nsD.L.
,e
ta1
.
,
Ph
ys.Che
m.
,1
992,
96(
23)
,91
06 [
1
5】 Xi
ng
X.P.
,Ti
n a
Z.X.
,Li
u H.T.
,e
t
a1
.
,
Phys
.Ch
em.
A,2003,
107(
41
)
,8484
【
1
6】 Dunc
n M.A.
a
,Kni
ghtA.M.
,Ne
gi
s
hiY.
,eta1
.
,
eh
ys
.Che
m.
A,
20
01
,105(
44)
,1
0093
【
1
7】 Pa
n de
y R.
,Ra
o B.K.
,J
ena
P.
,e
t
a1
.
,
Am.Che
m.S
O c.
,2001,
1
23(
16
)
,3799
【
18
】 Ra
o B.K.
,J
ena
P.
,
Che
m.P噍 .
,
2Oo
2,
』7(
11
)
,
5234 【
19
】 Wu D.Y.
,Re
n B.
,J
i
n g a
Y.X.
,e
t
a
1
.
,
Ph
ys.Che
m.A,20
02,
1
06(
39)
,9
042 【
20】 Ka
n da
l
a
m A.K.
,Rao B.K.
,J
e
na P.
,e
t
a1
.
,
Chem.eh
ys
.
,2004,
1
20(
22)
,1
041
4
【
2 1
】 Lu
t
t
ge
ns
G.
,Po
nt
i
us
N.
,Ff
ie
dr
i
c
h C.
,e
l
a1
.
,
Che
m.Ph
ys
.
,2001
,
114(
1
9)
,8
41
4
【
22】 Ge
r
har
ds
M.
,Tho
ma
s
O.C.
,Ni
l
l
e
s
J.M.
,e
t
a1
.
,J=Che
m.Ph
ys.
,
20
02,116(
23)
,1
0247
【
23】 ZhengW…J
Ni
l
l
e
s
J.
M.
,T
h oma
sO.C.
,e
ta1
.
,Che
m.Ph
ys
.Le
t
t
.
,
2
伽I
5,卯 ,(
1
— 3)
,266
【
24
] Zhen
g W …J
Ni
l
l
es
J
.M.
,T
h oma
s O.C.
,e
t
a1
.
,
Ch
em.Ph
ys
.
,
2o05,12
2(
4)
,
44306
【
25
】J
udai
K.
,Hi
r
n o a
M.
,Kawama
t
a H.
,e
t
a1
.
,Chem.Ph
ys
.Le
t
t
.
,19
97
,
27
0(
1
/
2)
,23
【
2
6】 J
ac
ks
on G.S.
,whi
t
e
F.M.
,Ha
mmi
l
l
C.L.
,et
a1
.
,J=Am.Chem.
So ,1
99
7,11
9(
32
)
,7567
【
27] Ber
g C.
,Bey
er
M.
,Ac
ha
t
z
U.
,et
aL,
Chem.Ph
ys
.
,199
8,1
08(
13
)
,
5398 2004,108
(
6)
,9
78 [
34] La
rs
on J.W .
,Mc
Ma
hon T.B.
,J=
Am.Che
m.S
o c.
,198
3,lO5(
1
o)
,
2944
【
35】 La
rs
on J.W.
,Me
Ma
hon
T.B.
,
Am.Che
m.S
o c.
,l
984,』D
3)
,
5l7 【
36】 Fr
e
nch
M.A.
,I
k
ut
a
S.
,Ke
ba
rl
e
P.
,Can.J=Che
m.
,1
982,60
(
15)
,
l907 【
37】 Xi
ng
X.P.
,Ti
n a
Z.X.
,Li
u P.
,e
t
a1
.
,Chi
n.J=Che
m.Ph
ys
.
,20
02,
15(
2)
,8
3 【
38
] Ti
n a
Z.X.
,Xi
n
g X.P.
,Ta
n g Z.C.
,Ra
pi
d Commun.Ma
ss S
pec
—
t
r
om.
,2oo2,16(
1
6)
,1
51
5
【
39
】 Ti
n a
Z.X.
,Xi
ngX.P.
,Ta
n g Z.C.
,Ra
pi
dCommu
n.Ma
s
s
S
pec
—
t
ro
m.
,2003,17
(1
)
,1
7
【
40】 Li
u H.T.
,Su
n S.T.
,Xi
n
g X.P.
,e
t
a1
.
,Ra
pi
d Commun.Mas
s
S
pec
 ̄om.
,
2006,2O(
1
2)
,18
99 【
41
】 De
n J
a
.A.
,Lan
ge'
s Handbook
o
fCh
emi
s
t
r
y 1
5t
h Ed.
,McGr
a
w-
Hi
l
l
Ine.
,New York,1999 【
42】 Col
me
na
re
s
F.
,To
r
r
ns
a
H.
,
Ph
ys.Che
m.A,2o05,10
9(
46
)
,
l0587 【
43】 Re
i
nho
l
d
M.
,Mc
Gr
a
dy
J
.E.
,Per
ut
z R.N.
,J=Am.Che
m.S
oc
.
,
20
o4,
2 1
6)
,52
68
【
44
] Ger
rd a
H.
,Davi
ds
on
E.
R.
,
Ei
s
e
ns
t
ei
n
O.
,Mo
1
.Ph
ys.
,20
02,1
00(
4)
,
533 【
45
】 d
e J
ong G.T.
,Bi
cke
l
ha
upt
F.M.
,
J=Ph
ys
.Che
m.A,
20
05,109(
42)
,
9685 【
4
6] Li
u X…J
Zha
n g X.
,Ha
n K.L.
,e
t
a1
.
,
Ph
ys
.Chem.A,2007,
11
1(
17
)
,3248
【
28】 Xi
n
g X.P.
,Li
u H.
T.
,Tang Z.C.
,
Ph
ys
che
mc
omm,200
3,
8)
,
32 [
47】 Bel
Br
uno
J.
J.
,Sur
f Sci
.
,20
05,577
(
21
3
)
,1
67
【
29] Sun S.T.
,Xi
ng X.P.
,Li
u H.T.
,et
a1
.
,
Ph
ys
.Che
m.A,2005,
【
4
8】 Ma
t
t
a
rS.M.
,Ha
mi
l
t
o
nW .
,
J=
Ph
ys
.Che
m.
,19
89,93(
8
)
,299
7