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| 0159611001. 今日化学 |
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1989 4 3 1
s j
1/2
I V exp(-Aj s) (1)
b
1
V j j + j
b 1 2
2
j j A
1 2
TTF-TCNQ tetrathiafulvalene tetracyanoquinodimethaneBEDT-TTF bis ethylenedithio tetrathiafulvalene
RecA-DNA DNA
HPI Hexagonally Packed Intermediate
1989 4 6 1
3 1 3
Au + CO Au O + C
2 2 3
4 2 4
F
SiC + 2H Si + CH G = +59kJ / mol
2 4 298
F
2Cu + CO 2CuO + C G = +140kJ / mol
2 298
F g v 1
T =
2 2
G G = G - G G
T T T
1 1
G G = -RT lnK - lnK K
p p p
G = H - H - T S -S = H T S
T T T T T T T
T C - Cp
P
S = S - S = S + dT
T T T 0
0
T
cp S S 0
0 T
298
1
2 2 2
BaO BaO + O
2
2
2
2 3 4 2
3 1 3
2
Au + CO Au O + C
4 2 4
2 2 3
2 4
1990 5 5 1 1989 10 18 70
Noyes Sherrill A Course of Study in Chemical Principles 1922—1938
1993 8 1 1
1993 8 3 4 1992 12 10
1993 8 4 1
+ +
Li Li Li 2(h )
2 2 2
+ -
Li + Li + h Li + e
2
ü
1988 3 1 1
1988 3 3 1
n+ (n-1)+ +
M(H O) = [M(H O) (OH )] + H
2 x 2 x-1
1988 3 6 1 1988 3 5 4 1989 4 5 1
1988 3 3 5
1990 5 6 5
- -
NO NO
3 3
1991 6 1 1
-
NO
3
1992 7 2 1
60 70
60 70 100
200
60 70
60 70 76 78
60 70 78 84
ppm ppm
3 c
o
3
2
1.5 1.5
2
2
3
2
2
3
1992 7 3 14 Yearbook of Sciences and the Future 1986 1990
1993 8 1 7
- G nFE
= = E F
- H - H
r m r
1
H + O = H O
2 2 2
2
4 2 2 2
3
CH OH + O = CO + 2H O
3 2 2 2
2
1
CO + O = CO
2 2
2
2 2 2 2 2
2 2 2
1
HCOOH aq + O = CO + H O
2 2 2
2
2 4
3 4
2 2 3
2-
2CO + 2CO 4CO + 4e
3 2
2-
O + 2CO + 4e 2CO
2 2 3
- 2-
CH OH + 8OH CO + 6H O + 6e
3 3 2
1993 8 6 11
1994 9 1 6
2 2
Ng 10 + exp(-3J / kT)
X = (2)
m
4kT 2 + exp(-3J / kT)
1994 9 3 1
2 2 3
2 2 3
2 2 3
2 2
2 2 2 3
2 4 2 3
3 2 3
2 3 3
2 3 3
3 2 3
2 3 2 3 S 2 S
3 3 2 3
2 2 4 7 3 2 4
4 2
1994 9 4 1
1994 9 6 1
dG = -SdT + Vdp + dn
i i
dG = dn , = T p + RT1nx
i i i 0 i
i
G = ni i = nA A + nB B+ nc c
2
2 2
2 2
2 2
2
2
2 2
2 4
2
2
2
2 n
2 n
2 n
12 12 4 2 2 n
1995 10 1 6
1986 1 4 1
2
r
0
i = 4 nFDC r +
o
Dt
2
r
1/2 0
r t >>
0
D
D nF
1/2
= ( ) = v
2
RT
ar
0
1990 5 4 1
12 g/ml
2
1990 5 5 4
600nm5 600nm73 400 500nm 90
300nm21% 300nm40% 200 1100nm 10%
1991 6 3 3
1991 6 6 1
1993 8 2 6
2 2 2 2 2
3 3 2 2 2
2 2 2
1987 2 2 9
6 11 6 6
6 5 6 5
6 5 6 5 3 7 3 7
6 5 6 11 6 11
6 11 6 11
6 5 2 5 3 7 3 7
3 7 3 7
3 7 3 7
3 7 3 7
6 5 6 5 6 5 6 5 3
6 5 6 5 6 5
1987 2 3 5
1987 2 4 3
-66
1987 2 4 7
1987 2 6 1
N N
sin(s r )
mn
I (s) = f f (1)
e.u. m n
s r
m m mn
n 0
sin(s r )
n
2
I (s) - Nf [1+ ] (2)
e.u.
s r
n n
￥
sin(s r)
2 2
I (s) = Nf [1+ 4 r (r) dr] (3)
e.u.
0
s r
￥
I (s) / N
e.u.
-1 = i(s) si(s) = 4 r ( r)sin(s r)dr
2
0
f
￥
1
Fourier r ( r) = si(s) sin( r s)ds (4)
2
0
2
￥
I (s)
0
2
2 r a s( ) sin( r s)ds I s
2 e. u.
0
Nf
2 3 [ 3 I s I s ] 4
e.u. 0
2 2
2 r[ ( r) - ] + 2 r =
a a
￥ ￥
I (s) sI (s)
e.u. 0
2
s[ -1]sin(r s)ds + sin(r s)ds 2 r[ (r) - ]
2 2 a
0 0
Nf Nf
￥
= si(s) sin( rs)ds
0
￥
2r
2 2
G(r ) = 4 r (r) = 4 r + si(s) sin( rs)ds (5)
a
0
￥
2r
2
DRDF = 4 r [ ( r) - ] = si(s)sin(rs)ds (6)
a
0
￥
DRDF 2
RRDF = P( r) = = si(s)sin(r s)ds (7)
0
r
I (s)
e.u. 2
- < f >
I (s) / N
N e.u.
i(s) = = -1
2 2
< f > < f >
2 2 2 2
< f >= x f x i < f > = ( x f )
i i i i i
i i
f (s) f (s) = k f (s) f (s) = f (s) / Z Z i
e i i e e i i i
i i
k i s
i
s
max
k = [fi(s) / fe(s)]ds / (s - s ) f (s) = k fe(s) g (r)
i max min i i i
s
min
r g r g (r) = ( x k ) (r ) 7
i i i i
i
I (s)
e .u. 2
- < f >
￥
2
N
4 r[ (r ) - ] = s[ ] sin( r s)ds
a 2
2
0
f
( x k )
e
i i
i
￥
2
P(r ) = 4 r( x k [g (r) - g ] = si(s) sin( r s)ds 8
i i i e
0
i
I (s)
e.u.
2 2
i(s) = [ - < f >] / f g ( x k )
i
e e i a
N
i
￥
2
4 r( N k )[g (r) - g ] = si(s)sin(r s)ds
i i i e
0
i
￥
2
4 r k [g ( r) - g ] = si(s)sin(r s)ds (9)
m m e
0
m
2 2
i(s) = [I (s) - f ] / f 9 Warren
e.u. m e
m
s s
max max
2 2 2 2 2
a = [s B(s) / f (s)]ds - 2 k g / [s I (s) / f (s)]ds
e m e e
s s
min min
m
2
B(s) = [f (s) + RC (s)] C s
m m m
m
s
2 max
8 P(r) si(s) sin(r s)ds (10)
s
min
8 1
r = R
j
3 s
max
P (r ) = (-4 g k ) r f s C s
L e m m m
m
2
az
0.6nmP r s s e
i
1988 3 2 8
2 2
4 2
2
2 2
2 7 2
2
3
2 3
1990 5 1 1
3 4
2
3 3
2 2
2 3 2
i
t - BuOOH Ti OP 4
r
1990 5 2 1
6 2
CH d - ML CH
3 4 2
3
8 7 6 5 4
2
7 6 5 4 3
6 5 4 3
3 2
5 4 3
5 5
2 5 5 5 5
3 5 5 2 5 5 2 5 5
2 5 5
5 5
4 5 4
3 2 3
5 5 5 5 6 6
3 2 3 2
3 2 2 9 11 2 2 9 11 2 2 9 11
5 5 2 3 2 5 5
3 2
5 4 3
2 5 5 5 5 5 5
3 2
1992 7 5 1
1992 7 6 4
1 1 1
K =
c
b K b
c c c
-
O O
2 2
-
O
2
T
1
DA
1992 7 6 12
D
6 5
3 6 5
6 5
3
6 5
3
3 3
6 5 3
3
3
3
1 2 3 3
2 C- C- C-S - S- C
2 1
2 2
- C - C C C
+
NH
3
1994 9 2 1
lgK 18.4 19.2
2+
UO
2
lg K / K = 10.6 17.0
2+ n+
UO M
2
lgK = 3.1 3.2
4 2+ 5 6
UO
2
1994 9 5 1
+
CH CH 4 CH N (CH )
2 2 3 2 10
c s cs c s 2 10 - Br
cs c s
a
1995 10 2 1
ü
1995 10 5 1
i
= S =
i
i i i
1986 1 1 3
4 2 3
= S = + + = 2
i
4 4 6
4 3 7
+ = 2 Al / Si 1
4 4 4
2- 2n-
[TiO ] [TiO ]
3 3 n
2-
P PO P - O 0.15nm ATP
3
R R - R
-N - 0
S = ( ) S = e ( )
R B
0
R
2
s
1
O H O H S +S = 1 1
1 2
R R
1 2
0.10 1.835
O V O V V O V S = 5.07
2 5
R 1 =10-1nm
3- 2+
2 VO 3 VO
4
2-
1.0v.u. SO O
4
3- -
PO ClO S 0.25 0.08v.u. 1 2
4 4 b
-
5- -
H PO ClO
IO
2 4 4
6
-
-
2-
BrO
H TeO CH CO
4
4 6 3 2
3-
2- -
BO
3 H SiO HCO
3 4 3
3
-
-
3 -
H TeO HCO
SiO 5 6 2
4
3-
3- 2 -
TeO
6
PO SO
4 4
3-
2- -
HSiO
4
HPO CF CO
4 3 2
2 4
2-
2- -
HBO
3
CO HSO
3 4
3
2 -
H SiO -
2 4
NO
3
-
H BO
2 3
2
+ 2-
Na SO S S 0.16 0.17
4 a b
3- 4- 5-
Li Rb Cs PO SiO AlO O S
4 4 4 b
2- -
0.25 0.33 0.42 SO ClO S
4 4 b
S S
1 2
O H O H 1 1 =
dlnS dln(1- S )
dR 1 1
1 1
= -B[ - ] = -B[ - ]
dS dS d(1- S ) S 1- S
1 1 1 1 1
(1- S ) -S (1- 2S )
1 1 1
= -B = -B
S (1-S ) S (1- S )
1 1 1 1
R N B R N B R N B
0 0 0
H 0.87 2.2 Be 1.374 0.38 Li 1.292 0.48
B 1.366 0.37 C 1.37 4.4 N 1.43 4.0
Na 1.661 0.44 1.40 0.26 1.41 0.39
Mg 1.636 0.42 Al 1.644 0.38 Si 1.63 0.36
P 1.62 0.36 Cl(VII) 1.622 4.7 S(VI) 1.614 0.36
K 2.276 9.1 S(IV) 1.629 4.6 Ca 1.09 5.4
1.84 0.48 Sc 1.865 5.4 1.896 0.41
Ti(IV) 1.806 5.2 1.877 0.35 V(V) 1.791 5.1
1.78 0.43 Ti(III-IV) 1.823 0.324 1.81 0.34
V(IV-V) 1.770 5.2 V(III-V) 1.790 0.319 Cr(VI) 1.787 5.0
Cr(III-VI) 1.772 0.315 Cr(V) 1.769 5.2 Cr(IV) 1.770 5.2
Cr(III) 1.733 5.2 Mn(VII) 1.780 5.43 Mn(IV) 1.774 5.2
Mn(III) 1.769 5.5 Mn(II) 1.798 5.6 Fe(III) 1.780 5.7
Fe(II) 1.764 5.5 Co(IV) 1.770 5.7 Co(II) 1.727 5.6
Ni(II) 1.680 5.4 Cu(II) 1.718 6.0 Zn(II) 1.675 0.39
Ga(III) 1.73 0.38 Ge(IV) 1.75 0.33 As(V) 1.77 0.41
Se(VI) 1.775 5.0 Rb 2.22 7.0 Se(IV) 1.796 4.0
Sr 2.143 7.0 Y(III) 2.070 7.0 Zr(IV) 1.950 6.0
Nb(V) 1.907 5.0 2.047 0.34 Zr(III-IV) 1.962 0.326
Nb(III-V) 1.921 0.319 Mo(II-VI) 1.882 6.0 Mo(III-VI) 1.890 0.314
Mo(VI) 1.90 0.33 Ag(I) 1.946 7.4 Mo(II) 1.835 5.0
Cd 1.990 7.4 In(III) 1.959 7.0 Sb(V) 1.911 6.0
Sb(II) 1.910 4.5 Sn(IV) 1.955 8.1 Sn(II) 1.860 4.5
Te(VI) 1.911 7.0 Te(IV) 1.933 4.5 I(VII) 1.942 5.8
I(V) 1.967 4.5 Xe(VI) 1.971 4.5 Cs 2.335 6.6
Ba 2.297 7.0 La(III) 2.167 6.5 Ce(IV) 2.117 0.326
Pr(IV) 2.099 0.325 2.200 0.339 Ce(III) 2.160 6.5
Pr(III) 2.150 6.5 Nd(III) 2.137 6.5 Pm(III) 2.120 6.5
Sm(III) 2.107 6.5 Eu(III) 2.090 6.5 Gd(III) 2.077 6.5
Tb(IV) 2.017 0.323 Tb(III) 2.065 6.5 Dy(III) 2.053 6.5
Ho(III) 2.041 6.5 Er(III) 2.029 6.5 Tm(III) 2.020 6.5
Yb(III) 2.012 6.5 Lu(III) 2.004 6.5 Hf(IV) 1.955 0.325
Ta(V) 1.907 5.0 W(VI) 1.904 6.0 Ta(III-V) 1.918 0.318
W(III-VI) 1.898 0.315 Re(VII) 1.910 6.0 Hg(II) 1.983 6.5
T1(III) 2.000 6.0 T1(I) 2.100 6.0 Pb(II) 2.044 5.5
Bi(III) 2.010 5.0 Ac(III) 2.29 0.35 Th(IV) 2.181 0.35
Pa(V) 2.11 0.35 U(VI) 2.059 4.3 Pa(IV) 2.147 0.35
U(V) 2.10 0.35 U(IV) 2.126 0.35 Np(VII) 2.06 0.35
Np(VI) 2.07 0.35 Np(V) 2.09 0.35 Np(IV) 2.11 0.35
Pu(VII) 2.05 0.35 Pu(NI) 2.06 0.35 Pu(V) 2.08 0.35
Pu(IV) 2.094 0.35 Pu(III) 2.142 0.35 Am(VI) 2.05 0.35
Am(V) 2.07 0.35 Am(IV) 2.083 0.35 Am(III) 2.131 0.35
Cm(IV) 2.077 0.35 Cm(III) 2.117 0.35 Bk(IV) 2.067 0.35
Bk(III) 2.103 0.35 Cf(IV) 2.056 0.35 Cf(III) 2.089 0.35
Es(III) 2.075 0.35
1986 1 2 1
= =
I
- cl
= 10
I
0
I
- c l
i i
= 10
I
0
v
ABC S S
0 1
v
ABC S + h ABC S
0 1
v v
ABC S ABC S ABC s
1 1 1
-( k t)
i
I = I e
t 0
1
t = =
k
i
I
0
I =
t
e
1
H O(1) H (g) + O (g)
2
2 2
2
1
CO g CO g + O g
2
2 2
3
N g + 3H O 1 2NH (g) + O (g)
2 2 3 2 2
1
H O l + O (g) H O (1)
2
2 2 2 2
3
CO g + 2H O(1) CH OH(l) + O (g)
2
2 2 3 2
2 2 4 2
1
NO + Cl NOCl
2
2
E = 0.21V
7 -2
i = 8.1 10 Am
1
H O l H g + O g
2 2 2
2
H = +295kJ / mol
G = +237kJ / mol( 2.46eV)
500nm
1987 2 1 1
. . 1983
. . 1983
Alan Holden Encyclopaedia Americana symmetry”
Proceedingsof11thNobelSymposium.1968
1987 2 2 5
1988 3 1 6
é
1988 3 4 6
1988 3 4 10
2
U = - (2a + 2r - d) (4a + 4r + d)
A 0
12
N
2
= kT (2)
0
V
b
V 1
2
d
1
2 1/2
(r )
d d
p
= 0 2 G = 0 2
2 1/2 2 1/2
(r ) (r )
V
2
V
2
V V V
2 2 2
V
2
V V
2 2
V V 1
2 2
V V
2 2
2 V V
2 2
2 2 2 2
2 2 2 2
b
V = 0.015
2
1989 4 2 1
2 2
2 1
1 2
E = -
6 2
3
Tr (4 )
0
2
a
2 1
E = -
2 6
(4 ) r
0
3 I I a a 1
1 2 1 2 2
E = - ( )( )
6
2 I + I 4
r
1 2 0
A B
E = -
12 6
r r
- +
COO H N
3
3
V
m
2
S = 0.162 N (nm / g)
g 0
V W
1990 5 4 9
N
K
cij
0 2
E = (l - l ) (2)
c ij ij
2
iM
K
bij
0 2
E = ( - ) (3)
b ij ij
2
i< j
0 0
ij ij ij ij
K
ij
0 0 0
E = (l - l + l - l )( - ) (4)
sb i i j j ij ij
2
i
0
3 0
ij
1
E = V (1- cos(i )) (5)
t j
2
3
V = / D r (cosX - 3cos a cos a ) (8)
dipl i j ij i j
i< j
V = q q / D r (9)
q i j ij
i< j
1991 6 2 5
-[2] - P1
210 210
1991 6 4 1
1
2 2 2 2 2 2
H = (P + P + x + y ) (1)
x y x y
2
é
1
2 2 2 2 2 2 2 2
H = P + P + x + y + x y + kx 2
x y x y
2
é
1993 8 6 1
- - - 2- -
Cl SCN H PO SO ClO
2 4 4 4
- 2- -
HSO SO H PO
4 4 2 4
2-
CO CO CO CO
ad 2 3
- -
AUGER 100 HSO ClO
4 4
1993 8 6 5
1995 10 1 1
1995 10 2 6
-
AMT HNO NO HDN
3 3
1995 10 4 1
1987 2 3 11
2
2+
Co H O
2 6
1990 5 3 6
3
2
2
t
1992 7 1 1 1990 10 19
MbO = Mb+ O Hb(O ) = Hb + nO
2 2 2 n 2
n
[Mb][O ] (po )
2 2
K = Y =
n n
[MbO ] (Po ) + (p )
2 2 50
[MbO ] Y po
2 2
Y = =
[MbO ] + [Mb] 1- Y p
2 50
[O ] po
2 2
Y = Y =
[O ] + K po + p
2 2 50
po
2
Y =
po + p
2 50
1992 7 2 7
0
2.3R S
-1
T = IgC +
M 0 T 0
H H
-1 0 0 0 0 0
T - lgC H S G = H - T S
M T T
0
G 37 1mol / L NaCl
T
0
=
( )
0 0 0
G - G G
( ) ( )
0
G = a + bn + ch a b c n h
37
1992 7 4 17
1993 8 4 9
1993 8 5 1
1994 9 1 1
1987 2 6 8
1988 3 2 3
CERN L3
16 7000 300
11 BGO
1991 6 5 1
1993 8 1 4
1993 8 1 5
1993 8 2 1
+ 2 3 2 2
[Fe C Me ] S = 1 / 2 a e [d ] (d - y )
5 5 2 1g 2g z 2
x
2
(d ) 3 e2g [TCNE] b3g S = 0
xy
2- 2 2
[TCNE] S = 1 a e 3
1g g gs
1993 8 5 5
C
E = h = h (1)
= - i = (1- itg ) (2)
e
= - i = (1- itg ) (3)
tg = (4)
e
tg = (5)
+ i = (7)
f
2 2 2
= [2(1+ tg tg ) + tg +
r r e e
2
1 1
2
2 2
tg ] + tg tg - 1] (8)
e
= (9)
r r
tg = tg
e
1994 9 5 6
1994 9 6 8
1995 10 3 6
2 3 2
2 3
3
3
12 19
5
5 4 3
2 2
2 14
2 3 7-
1987 2 3 1
1987 2 2 1
1987 2 5 4
kcal/mol 1987 1kcal/mol=4.184kJ/mol
1988 3 5 1
1989 4 4 5
1989 4 4 7
1990 5 3 1
1990 5 3 2
1991 6 2 1
1992 7 3 9
+￥
-i t
S( ) = s(t)e dt (1)
-￥
+￥
1
i t
s(t) = S( )e d (2)
2
-￥
S / N T (7)
tot
1993 8 3 1
2
( G + )
2 1
2 1/2 0
k = H [ ] exp[- ] (1)
et DA
h 4 RT 4 RT
2
e 1 1 1 1 1
= [ + - ][ - ] (3)
4 2r 2r r
0 D A DA op s
1994 9 3 6
é
é
1995 10 3 1
ppm
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