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a
H2 CO <br />
N2 520
e −H2 e −CO e −N2 520
e −H2 e −CO e −N2 520
e −H2 e −CO e −N2 520
e −H2 e −CO e −N2 520
e −H2 <br />
e −CO <br />
e −N2
e −H2 <br />
e −H2 <br />
e −H2 <br />
e −H2 <br />
e −CO <br />
e −CO <br />
e −CO <br />
e −N2 <br />
e −N2 <br />
e −N2
SiH4 GeH4 CF4 <br />
<br />
<br />
<br />
H2 N2 CO
ST O − NG DZV <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
1 <br />
2
e −H2 e −N2 e −CO <br />
5 20 <br />
• e −H2 <br />
<br />
• N2 CO <br />
<br />
<br />
<br />
<br />
e −H2 DZV <br />
e −N2 e −CO DZV <br />
<br />
< 20 DZV
E0 <br />
<br />
• <br />
• <br />
• <br />
• <br />
e − (Eo) + AB → e − (Eo) + AB<br />
e − (Eo) + AB → e − (Eo − ∆E) + AB ∗<br />
e − ⎧<br />
⎨ (AB)<br />
(Eo) + AB →<br />
⎩<br />
+n + (n + 1)e− A +nB +m + (n + m + 1)e− e − (Eo) + AB → A + B + e − .
AB ∗ <br />
<br />
(AB) +n A +n B +m <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
V () r <br />
<br />
<br />
<br />
<br />
V ()
V () <br />
<br />
( Ho + V )|ψ〉 = E|ψ〉, <br />
Ho = 1<br />
2 ∇2 |ψ〉 <br />
V () <br />
V = 0 <br />
V = 0 H <br />
<br />
<br />
Ho |φ〉 <br />
Ho <br />
Ho|φ〉 = E|φ〉, <br />
<br />
<br />
1<br />
|ψ〉 = |φ〉 +<br />
E − V |ψ〉 <br />
Ho<br />
V → 0 |ψ〉 → |φ〉 <br />
1<br />
<br />
E <br />
E − Ho<br />
<br />
<br />
|ψ ± 1<br />
〉 = |φ〉 +<br />
E − V |ψ<br />
Ho ± iε<br />
± 〉, <br />
ε ≪ 1 ± <br />
<br />
<br />
<br />
<br />
〈|ψ ± <br />
〉 = 〈|φ〉 +<br />
d 3 x ′ 1<br />
〈|<br />
E − Ho ± iε |′<br />
〉〈 ′<br />
| V |ψ ± 〉
〈|ψ ± <br />
〉 = 〈|φ〉 +<br />
d 3 p ′ 1<br />
〈|<br />
E − Ho ± iε |′<br />
<br />
〉〈 ′<br />
| V |ψ ± 〉. <br />
<br />
G±(, ′<br />
) <br />
G±(, ′<br />
) = 2<br />
2m 〈|<br />
1<br />
E − Ho ± iε |′<br />
〉, <br />
2 /2m <br />
<br />
<br />
<br />
〈|〉 = ei·/<br />
(2π) 3/2<br />
<br />
Ho = 2<br />
, <br />
2m<br />
G±(, ′<br />
) = − 1 1<br />
4π | − ′ | e±ik|−′ | p<br />
, k =<br />
<br />
<br />
<br />
<br />
(∇ 2 + k 2 )G±(, ′<br />
) = δ( − ′<br />
). <br />
〈|ψ ± 〉 = 〈|φ〉 − 2m<br />
2<br />
<br />
d 3 x ′ e±ik|−′ |<br />
4π| − ′ | 〈′<br />
| V |ψ ± 〉.<br />
<br />
〈|ψ ± 〉 <br />
〈|φ〉 <br />
<br />
e ±ikr /r
V <br />
<br />
〈 ′<br />
| V |ψ ± <br />
〉 =<br />
〈 ′<br />
| V | ′′<br />
〉 = V ( ′<br />
)δ( ′<br />
− ′′<br />
), <br />
d 3 x ′′<br />
〈 ′<br />
| V | ′′<br />
〉〈 ′′<br />
|ψ ± 〉 = V ( ′<br />
)〈 ′<br />
|ψ ± 〉. <br />
<br />
〈|ψ ± 〉 = 〈|φ〉 − 2m<br />
2<br />
<br />
d 3 x ′ e±ik|−′ |<br />
4π| − ′ V (′ )〈<br />
| ′<br />
|ψ ± 〉, <br />
<br />
<br />
• <br />
<br />
• V
|| ≫ | ′<br />
| <br />
<br />
r = || <br />
<br />
|r| ≫ |r ′<br />
| <br />
<br />
r ′<br />
= | ′<br />
|, <br />
| − ′<br />
| r − . ′<br />
, = <br />
. <br />
||<br />
′<br />
= k, <br />
′<br />
<br />
r <br />
<br />
<br />
<br />
<br />
e ±ik|−′ | = e ±ikr e ∓i ′ . ′<br />
. <br />
1<br />
| − ′ |<br />
1<br />
r = i <br />
<br />
<br />
〈|φ〉 = 〈|〉 = ei<br />
(2π) 3 , <br />
2<br />
〈| ′<br />
〉 = δ( − ′<br />
), <br />
i <br />
<br />
<br />
〈|ψ ± 〉<br />
r gran<strong>de</strong><br />
−−−−→ 〈|φ〉 − 1<br />
4π<br />
2m<br />
2 eikr <br />
r<br />
d 3 x ′<br />
e −i′ . ′<br />
V ( ′<br />
)〈 ′<br />
|ψ ± 〉, <br />
〈|ψ ± 〉 = 1<br />
(2π) 3 [e<br />
2<br />
i. + eikr<br />
r f(′ ,)],
f( ′<br />
,) = − (2π)3/22m 4π2 <br />
= − (2π)3/2 2m<br />
4π 2<br />
<br />
d 3 x ′<br />
e −i′ . ′<br />
V ( ′<br />
)〈 ′<br />
|ψ ± 〉<br />
d 3 x ′<br />
e −i′ . ′<br />
〈 ′<br />
| V |ψ ± 〉,<br />
<br />
<br />
f( ′<br />
2 2m<br />
,) = −2π<br />
2 〈φk ′| V |ψ ± 〉. <br />
ei. eikr<br />
r f(′ ,) <br />
<br />
f( ′<br />
,) <br />
<br />
<br />
<br />
f( ′<br />
,) <br />
|ψ ± 〉 <br />
<br />
<br />
<br />
<br />
〈 ′<br />
|ψ + 〉 −→ 〈 ′<br />
|φ〉 = ei.′<br />
(2π) 3 . <br />
2<br />
<br />
f( ′<br />
,) = − 1 2m<br />
(2π)3<br />
4π 2 = − 1 2m<br />
(2π)3<br />
4π 2 <br />
<br />
d 3 x ′<br />
〈 ′<br />
| ′<br />
〉〈 ′<br />
| V |ψ + 〉<br />
d 3 x ′ e−i′ . ′<br />
(2π) 3<br />
2<br />
〈 ′<br />
|ψ + 〉V ( ′<br />
)<br />
<br />
3 |ψ + 〉 <br />
|ψ − 〉
f (1) ( ′<br />
,) = − 1 2m<br />
4π 2 <br />
<br />
d 3 x ′<br />
e i(−′ ). ′<br />
V ( ′<br />
). <br />
V <br />
− ′<br />
′<br />
<br />
|| = | ′<br />
| <br />
<br />
| − ′<br />
θ ′<br />
<br />
| = q = 2ksen( θ<br />
), <br />
2<br />
′<br />
<br />
<br />
f (1) (θ) = − 1 2m<br />
q 2 ∞<br />
0<br />
dr ′<br />
r ′<br />
V (r ′<br />
)sen(qr ′<br />
). <br />
<br />
<br />
<br />
<br />
〈|ψ + 〉 = 〈|φ〉 − 1<br />
4π<br />
2m<br />
2 eikr r<br />
<br />
d 3 x ′<br />
e −i′ . ′<br />
V ( ′<br />
)〈 ′<br />
|ψ + 〉,
〈 ′<br />
|ψ + 〉 <br />
V ( ′′<br />
) <br />
〈 ′<br />
|ψ + 〉 = 〈 ′<br />
|φ〉 − 1<br />
4π<br />
<br />
〈|ψ + 〉 = 〈|φ〉 − 1 2m<br />
4π 2 − 1 2m<br />
4π 2 r<br />
e ikr<br />
e ikr<br />
r<br />
<br />
<br />
2m<br />
2 eikr <br />
r<br />
d 3 x ′<br />
e −i′ . ′<br />
V ( ′<br />
)〈 ′<br />
|φ〉−<br />
d 3 x ′<br />
<br />
<br />
<br />
<br />
〈|ψ + 〉 = 1<br />
(2π) 3<br />
2<br />
<br />
d 3 x ′′<br />
e −i.′′<br />
V ( ′′<br />
)〈 ′′<br />
|ψ + 〉. <br />
d 3 x ′′<br />
e −i′ . ′<br />
V ( ′<br />
)e −i′ . ′′<br />
V ( ′′<br />
)〈 ′′<br />
|ψ + 〉. <br />
〈 ′<br />
|ψ + 〉 −→ 〈 ′<br />
|φ〉 = ei.′<br />
(2π) 3<br />
2<br />
<br />
〈 ′′<br />
|ψ + 〉 −→ 〈 ′′<br />
|φ〉 = ei.′′<br />
(2π) 3 , <br />
2<br />
<br />
e i. + eikr<br />
<br />
f<br />
r<br />
(1) ( ′<br />
,) + f (2) ( ′<br />
<br />
,)<br />
<br />
, <br />
f (1) ( ′<br />
,) f (2) ( ′<br />
,) <br />
f (2) ( ′<br />
,) = − 1 2m<br />
4π 2 <br />
d 3 x ′<br />
d 3 x ′<br />
e i′ . ′<br />
V ( ′<br />
)e i(−′ ). ′′<br />
V ( ′′<br />
). <br />
<br />
<br />
T <br />
V |ψ + 〉 = T |φ〉. <br />
V <br />
V |ψ + 〉 = V |φ〉 + 1<br />
V<br />
E − V |ψ<br />
Ho + iε<br />
+ 〉
T<br />
T |φ〉 = V |φ〉 + 1<br />
V<br />
E − T |φ〉. <br />
Ho + iε<br />
|φ〉 Ho <br />
<br />
<br />
<br />
T = V + 1<br />
V<br />
E − T . <br />
Ho + iε<br />
f( ′<br />
,) = − 1 2m<br />
(2π)3 〈′ |<br />
4π 2 V |ψ + 〉, <br />
f( ′<br />
,) = − 1 2m<br />
(2π)3 〈′ |<br />
4π 2 T |φ〉. <br />
|φ〉 Ho <br />
f( ′<br />
,) = −2π<br />
2 2m<br />
〈′<br />
2<br />
<br />
| T |〉. <br />
f( ′<br />
,) <br />
T <br />
<br />
T = V + 1<br />
V<br />
E − V +<br />
Ho + iε<br />
1<br />
V<br />
E − V<br />
1<br />
Ho + iε E − V + .... <br />
Ho + iε<br />
<br />
f( ′<br />
,) =<br />
∞<br />
n=1<br />
f (n) ( ′<br />
,), <br />
V <br />
<br />
<br />
f (1) ( ′<br />
,) = − 1 2m<br />
(2π)3 〈′ |<br />
4π 2 V |〉 <br />
f (2) ( ′<br />
,) = − 1<br />
4π<br />
2m<br />
(2π)3 〈′ |<br />
2 V<br />
1<br />
E − V |〉. <br />
Ho + iε
1<br />
2 ∇2 <br />
+ V () ψ() = Eψ(), <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
lmax<br />
mmax <br />
<br />
Ho |φ〉 ≡ |〉 <br />
<br />
<br />
〈|φ〉 = 〈|〉 = ei.<br />
(2π) 3 . <br />
2<br />
( Px, Py, Pz) <br />
Ho Pi
( Ho, 2, Lz) <br />
|E, l, m〉<br />
<br />
<br />
〈E ′<br />
, l ′<br />
, m ′<br />
|E, l, m〉 = δ(E − E ′<br />
)δ(l − l ′<br />
)δ(m − m ′<br />
) <br />
<br />
<br />
l<br />
m<br />
<br />
dE|E, l, m〉〈E, l, m| = . <br />
Ho {|E, l, m〉} <br />
<br />
Ho|E, l, m〉 = E|E, l, m〉. <br />
<br />
<br />
<br />
Ho[r, θ, φ]〈r, θ, φ|E, l, m〉 = E〈r, θ, φ|E, l, m〉 <br />
− 2<br />
2m ∇2<br />
rθφ〈r, θ, φ|E, l, m〉 = E〈r, θ, φ|E, l, m〉, <br />
− 2<br />
2m [1<br />
∂<br />
r<br />
2 1 1 ∂ ∂ 1<br />
r + ( (senθ ) +<br />
∂r2 r2 senθ ∂θ ∂θ sen2 ∂<br />
θ<br />
2<br />
2 )]〈r, θ, φ|E, l, m〉 = E〈r, θ, φ|E, l, m〉.<br />
∂φ<br />
<br />
〈r, θ, φ|E, l, m〉 <br />
<br />
〈r, θ, φ|E, l, m〉 = R(r)η(θ, φ). <br />
<br />
〈r, θ, φ|E, l, m〉 = cljl(kr)Y m<br />
l (θ, φ), <br />
4 φ
cl = il<br />
<br />
2mk<br />
<br />
jl(kr) Y π m<br />
l (θ, φ) <br />
|E, l, m〉 <br />
〈|E, l, m〉 = <br />
<br />
√ δ E −<br />
mk 2k2 <br />
Y<br />
2m<br />
m<br />
l ( ). <br />
|〉 |E, l, m〉 <br />
<br />
V = 0<br />
T V<br />
T L2 Lz <br />
<br />
T <br />
T (o)<br />
o = S <br />
〈α ′<br />
, j ′<br />
, m ′<br />
| 〈α<br />
S|α, j, m〉 = δ ′δ ′<br />
jj mm ′<br />
, j ′<br />
|| S||α, j〉<br />
√<br />
2l + 1<br />
{|E, l, m〉} T <br />
<br />
<br />
. <br />
〈E ′<br />
, l ′<br />
, m ′<br />
| T |E, l, m〉 = Tl(E)δ ll ′δ mm ′, <br />
Tl(E) = 〈E′ , l ′<br />
|| S||E, l〉<br />
√<br />
2l + 1<br />
f( ′<br />
,) <br />
f( ′<br />
,) = − 1 2m<br />
(2π)3<br />
4π <br />
= 1 2m<br />
(2π)3<br />
4π 2 <br />
= − 1 2m<br />
(2π)3<br />
4π 2 2 〈′<br />
| T |〉<br />
<br />
<br />
l,m l ′ ,m ′<br />
<br />
l<br />
m<br />
. <br />
dEdE ′<br />
〈 ′<br />
|E ′<br />
, l ′<br />
, m ′<br />
〉〈E ′<br />
, l ′<br />
, m ′<br />
|T |E, l, m〉〈E, l, m|〉<br />
Tl(E)| <br />
E= 2k2 Y<br />
2m<br />
m<br />
l ( ′<br />
)Y m∗<br />
l ( ),<br />
<br />
<br />
z θ ′<br />
<br />
Y m∗<br />
l<br />
( ) = Y m∗<br />
(θ = 0, φ)δm0 =<br />
l<br />
2l + 1<br />
4π δm0.
′<br />
Y m<br />
l ( ′<br />
) =<br />
m <br />
<br />
2l+1<br />
4π Pl(cosθ) <br />
f( ′<br />
,) = <br />
(2l + 1)fl(k)Pl(cosθ), <br />
<br />
l<br />
fl(k) = − πTl(E)<br />
. <br />
k<br />
|E, l, m〉<br />
<br />
〈|ψ (+) 〉 <br />
<br />
〈|ψ + 〉<br />
r gran<strong>de</strong><br />
−−−−→ 1<br />
(2π) 3 [e<br />
2<br />
i. + eikr<br />
r f(′ ,)]. <br />
<br />
<br />
e i. = 4π <br />
i l jl(kr)Y m<br />
l ( ′<br />
)Y m∗<br />
l ( ) <br />
l<br />
m
Y m<br />
l ( ′<br />
<br />
2l+1 ) = 4π Pl(cosθ) m <br />
<br />
e i. = <br />
i l jl(kr)(2l + 1)Pl(cosθ). <br />
l<br />
<br />
〈|ψ (+) 〉 <br />
〈|ψ + 〉<br />
r gran<strong>de</strong><br />
−−−−→ 1<br />
(2π) 3<br />
2<br />
jl(kr)<br />
<br />
l<br />
r gran<strong>de</strong><br />
−−−−→<br />
(2l + 1)Pl(cosθ)<br />
2ik<br />
π<br />
ei(kr−l 2 ) π<br />
−i(kr−l − e 2 )<br />
, <br />
2ikr<br />
e ikr<br />
r (1 + 2ikfl(k)) − e−i(kr−lπ)<br />
r<br />
<br />
. <br />
<br />
V = 0 fl(k) V l <br />
eikr <br />
<br />
r<br />
<br />
− e−i(kr−lπ)<br />
<br />
<br />
r<br />
V = 0 <br />
<br />
<br />
1 −→ (1 + 2ikfl(k)),
N M<br />
<br />
<br />
HΨ(x1, x2, ...xN; x) = EΨ(x1, x2, ...xN; x), <br />
E (x1, x2, ...xN; x) <br />
(x) <br />
H <br />
H = Hmol − 1<br />
2 ∇2 +<br />
M<br />
V (| − A|) +<br />
A<br />
<br />
N<br />
V ( − i), <br />
− 1<br />
2 ∇2 V (| − A|) <br />
V (| − i|) <br />
<br />
Hmol <br />
M<br />
<br />
Hmol = −<br />
A=1<br />
1<br />
∇<br />
2MA<br />
2<br />
A + <br />
<br />
ZAZB<br />
+<br />
|RA − RB|<br />
B
Hmol = <br />
<br />
− 1<br />
2 ∇2j − <br />
j<br />
A<br />
ZA<br />
rjA<br />
+ <br />
l
− 1<br />
2 ∇2 + Hmol + V<br />
<br />
<br />
A {|Φ〉 ⊗ |ψ〉} = E A {|Φ〉 ⊗ |ψ〉} . <br />
<br />
〈Φ| <br />
〈Φ|(− 1<br />
2 ∇2 )| A {|Φ〉 ⊗ |ψ〉} + 〈Φ| Hmol| A {|Φ〉 ⊗ |ψ〉} + 〈Φ| V | A {|ψ〉 ⊗ |ψ〉}<br />
= E〈Φ| A {|Φ〉 ⊗ |ψ〉} <br />
|Φ〉 Hmol <br />
ε <br />
(∇ 2 + k 2 )|ψ〉 = U|ψ〉, <br />
<br />
<br />
k 2 = 2E − 2ε <br />
U|ψ〉 = 〈Φ| V | A {|Φ〉 ⊗ |ψ〉} . <br />
U <br />
<br />
U = 2V S + 2V T . <br />
V S V T <br />
<br />
<br />
<br />
<br />
<br />
<br />
|ψ (±) 〉 = |φ〉 + G (±)<br />
0 U|ψ (±) 〉,
G0 |φ〉 <br />
|ψ (±) 〉 (+) <br />
(−)<br />
<br />
U <br />
<br />
<br />
V S HF ()ψ() =<br />
n<br />
<br />
2<br />
i=1<br />
V T HF ()ψ() =<br />
n<br />
i=1<br />
dr ′ ϕ i()ϕ i()<br />
| − ′ | +<br />
<br />
2<br />
M<br />
A=1<br />
ZA<br />
| − RA|<br />
<br />
<br />
ψ() <br />
dr ′ ϕi()ψi() | − ′ <br />
ϕ<br />
|<br />
i() <br />
ϕ i |Φ〉 U = 2 V S HF + 2 V T HF
f( ′<br />
<br />
,) = −2π 2 〈φ ′| k U|ψ (+)<br />
k 〉 <br />
f( ′<br />
,) = −2π 2 〈ψ (−)<br />
k ′ | U|φ k〉, <br />
U 2m V<br />
ℏ 2 <br />
<br />
f( ′<br />
,) = −2π 2<br />
|φk〉 = |ψ (+)<br />
k 〉 − G0 U|ψ (+)<br />
<br />
〈ψ (−)<br />
k ′ | U|ψ (+)<br />
k<br />
<br />
[f] = −2π 2<br />
<br />
〈φ ′| k U|ψ (+)<br />
k<br />
k<br />
〉 <br />
〉 − 〈ψ(−)<br />
k ′ | U G0 U|ψ (+)<br />
k 〉<br />
<br />
. <br />
〉 + 〈ψ(−)<br />
k ′ | U|φ k〉 − 〈ψ (−)<br />
k ′ | U − U G0 U|ψ (+)<br />
k 〉<br />
<br />
. <br />
<br />
δ[f] = 0 <br />
〈ψ (−)<br />
k ′ | |ψ (+)<br />
k 〉 <br />
<br />
[f] <br />
[f] <br />
<br />
|ψ (+)<br />
k<br />
〉 −→ A|ψ(+)<br />
k 〉 <br />
〈ψ (−)<br />
k ′ | −→ B〈ψ (−)<br />
k ′ |, <br />
A B <br />
<br />
[f] = 2π 2<br />
<br />
A〈φk ′| U|ψ (+)<br />
k<br />
〉 + B〈ψ(−)<br />
k ′ | U|φk〉 − AB〈ψ (−)<br />
k ′ | U − U G0 U|ψ (+)<br />
k 〉
[f] A B <br />
<br />
<br />
∂[f]<br />
∂A<br />
∂[f]<br />
∂B<br />
[f] = −2π 2 〈φ k ′| U|ψ (+)<br />
k 〉〈ψ(−)<br />
k ′ | U|φ k〉<br />
<br />
= 0 <br />
= 0, <br />
〈ψ (−)<br />
k ′ | U − U G0 U|ψ (+)<br />
k<br />
〉 . <br />
<br />
<br />
<br />
<br />
<br />
[T ] = − [f]<br />
, <br />
2π2 [T ] = 〈φ ′| k U|ψ (+)<br />
k 〉 + 〈ψ(−)<br />
k ′ | U|φk〉 − 〈ψ (−)<br />
k ′ | U − U G0 U|ψ (+)<br />
k<br />
[T ] = 〈φk ′| U|ψ (+)<br />
k 〉〈ψ(−)<br />
k ′ | U|φk〉 〈ψ (−)<br />
k ′ | U − U G0 U|ψ (+)<br />
k<br />
〉 <br />
〉 . <br />
<br />
δ[T ] = 0 [T ] T<br />
|ψ (±)<br />
k 〉 <br />
〈ψ (−)<br />
k ′ | |ψ (+)<br />
k 〉 <br />
<br />
δ [T ] = 0 <br />
<br />
ψ (+)<br />
k () ψ (−)<br />
k ′ () R0 {g}
ψ (+)<br />
k () = <br />
ψ (−)<br />
k ′ () = <br />
j<br />
i<br />
<br />
bi,klm()gi() <br />
cj,klm( ′<br />
)gj(), <br />
gi gj <br />
R0 ≡ {g1, g2, ..., gN} <br />
<br />
[T ] ′ = <br />
bi,klm〈φk ′| U|gi〉+ <br />
cj,klm〈gj| U|φk〉− <br />
bi,klmcj,klm〈gj| U − U G0 U|gi〉<br />
i<br />
j<br />
<br />
[T ] ′ <br />
bi,klm cj,klm <br />
<br />
∂[T ] ′<br />
∂bi,klm<br />
∂[T ] ′<br />
[T ] ′ <br />
<br />
∂cj,klm<br />
i<br />
j<br />
= 0 <br />
= 0. <br />
[T ] ′ = <br />
〈φ ′| k U|gi〉[D] −1<br />
ij 〈gj| U|φk〉, <br />
ij<br />
[D] −1<br />
ij = 〈gj| U − U G0 U|gi〉. <br />
{gi}<br />
<br />
<br />
|ψ (P ) 〉 = |φ〉 + G (P )<br />
0 U|ψ (P ) 〉.
K <br />
<br />
[K] ′ = <br />
〈φk ′| U|gi〉[D (P ) ] −1<br />
ij 〈gj| U|φk〉, <br />
ij<br />
[D (P ) ] −1<br />
ij = 〈gj| U − U G<br />
T <br />
<br />
(P )<br />
0 U|gi〉, <br />
T = −2iK<br />
. <br />
1 − iK<br />
K T R0<br />
ψ (±)<br />
k () <br />
{gi}<br />
<br />
<br />
R0 <br />
S0 =<br />
<br />
ψ R0 (), ψR0 (), ..., ψR0<br />
k,l1,m1 k,l2,m2 k,lp,mp ()<br />
<br />
, <br />
<br />
|ψ (±) 〉 = |φ〉 + G0 T |φ〉, <br />
T {gi} <br />
lp mp l <br />
m <br />
R1 = R0 ∪ S0 <br />
ψ (±) () R1 <br />
T (R1) ψ (±) () <br />
<br />
S1 =<br />
<br />
ψ R1 (), ψR1 (), ..., ψR1<br />
k,l1,m1 k,l2,m2 k,lp,mp ()<br />
<br />
.
R2 = R0 ∪ S1 <br />
ψ (±) () <br />
<br />
<br />
<br />
U = 2m<br />
2 V K <br />
[K] ′ = <br />
〈φ ′| k U|gi〉[D (P ) ] −1<br />
ij 〈gj| U|φk〉, <br />
ij<br />
{gi} Rn = R0 ∪ Sn−1<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
dσ<br />
dΩ<br />
<br />
= dNd<br />
η intdΩ = |f(f,i)| 2 , <br />
σ <br />
<br />
<br />
θ dσ(θ)<br />
dΩ
Nd η i <br />
nt dΩ <br />
f(f,i) <br />
<br />
<br />
|f(f,i)| = −2π 2 Tfi, <br />
T <br />
<br />
σt =<br />
<br />
<br />
dσ(θ)<br />
dΩ. <br />
dΩ
{χ} <br />
ϕ i = <br />
i<br />
<br />
cµiχ µ, <br />
ϕ i χ µ <br />
cµi <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
∗ d <br />
∗∗ d
p <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
DZV <br />
<br />
<br />
<br />
1s 2s 2p
H He Li Ne Na Ar <br />
K Ca Sc Kr <br />
<br />
<br />
N <br />
<br />
N <br />
<br />
<br />
<br />
<br />
<br />
<br />
DZV <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
H He Li Ne Na Ar <br />
DZV
Li F <br />
χ 1s() =<br />
χ ′<br />
2s() =<br />
χ ′<br />
2p() =<br />
4<br />
j=1<br />
3<br />
j=1<br />
<br />
dj,1sf1s(αj,1s,) <br />
d ′<br />
j,2sf1s(α ′<br />
j,2sp,) <br />
χ ′′<br />
2s() = f1s(α ′′<br />
2sp,) <br />
3<br />
j=1<br />
dj,2pf2p(α ′<br />
j,2sp,) <br />
χ ′′<br />
2p() = f2p(α ′′<br />
2sp,) <br />
dj,... α f1s f2p <br />
(8s4p/4s)/[3s2p/2s] <br />
s<br />
s <br />
χ ′<br />
1s() =<br />
3<br />
j=1<br />
d ′<br />
j,1sf1s(α ′<br />
j,1s,) <br />
χ ′′<br />
1s() = f1s(α ′′<br />
1s,). <br />
<br />
<br />
4 3 1 <br />
DZV <br />
<br />
<br />
DZV
DZV H2 <br />
(4s)/[2s] s <br />
s H2 (4s3p)/[2s3p]<br />
s <br />
p s p <br />
N2 (10s5p)/[3s2p] <br />
s p <br />
s p CO <br />
N2 DZV
DZV H2 <br />
(4s)/[2s] s <br />
s H2 (4s3p)/[2s3p]<br />
s <br />
p s p <br />
N2 (10s5p)/[3s2p] <br />
s p <br />
s p CO <br />
N2 DZV
S m l (θ, φ) rl <br />
<br />
χ(k, l, m) = Nl(ςk) (2l+3)/4 exp(−ςkr p )r l S m l (θ, φ) k = 1, 2, ..., <br />
Nl = 2 (4l+7)/4 π −1/4 [(2l + 1)!] −1/2 , <br />
p = 1 p = 2 <br />
ς <br />
<br />
ςk = αβ k−1 , k = 1, 2, ..., M. <br />
α β M <br />
<br />
• α <br />
α <br />
<br />
• β <br />
• M <br />
α β M <br />
<br />
α β <br />
1s <br />
2p <br />
3d
α β M <br />
l l <br />
M(l) −→ ∞ α(l) −→ 0 β(l) −→ 1 β(l) M −→ ∞<br />
9s1p <br />
e −H2 <br />
p = 2 <br />
<br />
<br />
<br />
1s <br />
2s <br />
3s <br />
4s <br />
5s <br />
6s <br />
7s <br />
8s <br />
9s <br />
1p <br />
(9s1p)<br />
• H2 CO N2<br />
• <br />
<br />
DZV <br />
• <br />
<br />
<br />
5
H2 CO N2 <br />
e −H2 9s1p<br />
(4s3p)/[2s3p] (10s5p)/[3s2p] <br />
e −CO 20s3p <br />
26s10p (10s5p)/[3s2p] e −N2<br />
26s10p (10s5p)/[3s2p] <br />
5
20<br />
<br />
<br />
H2 <br />
e −CO <br />
e −N2<br />
e −H2<br />
e −H2 <br />
<br />
<br />
EHF <br />
(4s3p)/[2s3p] <br />
(10s5p)/[3s2p] <br />
(9s/1p) <br />
EHF H2<br />
<br />
e −H2 <br />
<br />
<br />
lmax = 40 <br />
<br />
lmax = 16 <br />
M = 2
5 <br />
<br />
<br />
<br />
80 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −H2
10 <br />
<br />
<br />
<br />
60 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −H2
15 <br />
<br />
<br />
θ ≥ 40 o <br />
<br />
60 o <br />
<br />
<br />
SCD (10 -16 cm 2 sr -1 )<br />
4,0<br />
3,5<br />
3,0<br />
2,5<br />
2,0<br />
1,5<br />
1,0<br />
0,5<br />
0,0<br />
0 20 40 60 80 100 120 140 160 180<br />
Ângulo <strong>de</strong> Espalhamento (graus)<br />
BU; DZV; Base Dunning; Shyn and Sharp; Srivastava et al<br />
e −H2
20 <br />
<br />
> 50 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −H2
e −CO<br />
<br />
e −CO<br />
EHF <br />
(10s5p)/[3s2p] <br />
(20s/3p) <br />
(26s/10p) <br />
EHF CO<br />
<br />
<br />
lmax = 40 <br />
<br />
lmax = 20 M = 10 11 <br />
<br />
<br />
10 15 20 <br />
<br />
<br />
15
10 <br />
<br />
60 0 135 o <br />
20s3p 26s10p <br />
<br />
θ > 60 o <br />
< 45 o<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −CO
15 <br />
<br />
60 o ≤ θ < 135 o <br />
<br />
< 30 o <br />
> 130 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −CO
θ<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −CO
e −N2<br />
N2 <br />
<br />
EHF <br />
(10s5p)/[3s2p] <br />
(26s/10p) <br />
EHF N2<br />
<br />
e −N2 <br />
<br />
lmax = 40 <br />
<br />
lmax = 20 Mmax = 10<br />
11 g u <br />
<br />
<br />
5 20
5 <br />
<br />
<br />
90 o 130 o <br />
<br />
50 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −N2
10 <br />
<br />
<br />
<br />
<br />
<br />
80 o <br />
<br />
<br />
SCD (10 -16 cm 2 sr -1 )<br />
9<br />
8<br />
7<br />
6<br />
5<br />
4<br />
3<br />
2<br />
1<br />
0<br />
0 20 40 60 80 100 120 140 160 180<br />
Ângulo <strong>de</strong> Espalhamento (graus)<br />
BU(26s10p) DZV; Srivastava et al ; Shyn and carignan;<br />
Siegel et al ; Chandra and T<strong>em</strong>kin;<br />
e −N2
20 <br />
<br />
<br />
<br />
<br />
30 o <br />
135 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −N2
20 <br />
<br />
<br />
<br />
<br />
30 o <br />
135 o <br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
e −N2
H2 <br />
<br />
CO N2 <br />
<br />
E < 20 <br />
5 10 15 20
• <br />
θ > 30 o <br />
θ > 60 <br />
• E ≤ 10eV <br />
<br />
30 o 160 o <br />
<br />
<br />
<br />
<br />
<br />
• CO 20s3p<br />
26s10p <br />
<br />
<br />
<br />
• 15 e −CO <br />
<br />
θ ><br />
50 o <br />
<br />
<br />
• 10 20 e −N2
θ > 30 o<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
• <br />
<br />
α(l) <br />
<br />
<br />
<br />
<br />
• <br />
<br />
<br />
<br />
<br />
•
θ > 30 o<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
<br />
• <br />
<br />
α(l) <br />
<br />
<br />
<br />
<br />
• <br />
<br />
<br />
<br />
<br />
•
α <br />
β <br />
H <br />
H = <br />
<br />
H|Φ〉 = E|Φ〉, <br />
k<br />
<br />
1 <br />
h(k) +<br />
2<br />
l=k<br />
1<br />
, <br />
rkl h(k) <br />
1<br />
r kl = g(kl)
Φ = [(2n)!] 1<br />
2 A (ϕ1α) 1 (ϕ 1β) 2 ...(ϕ nα) 2n−1 (ϕ nβ) 2n , <br />
ϕη η = α β A <br />
<br />
<br />
E[ϕ1, ϕ2, ...ϕN/2] =<br />
<br />
<br />
Φ ∗ HΦdτ <br />
E[ϕ1, ϕ2, ...ϕN/2] = 2 <br />
h(i) + <br />
(2Jij − Kij), <br />
i<br />
Jij |ϕ i| 2 |ϕ j| 2 <br />
Kij exchange <br />
<br />
Jij =<br />
Kij =<br />
<br />
<br />
hi =<br />
<br />
i,j<br />
ϕ ∗ i (µ)h(µ)ϕ i(µ)dτ µ, <br />
ϕ ∗ i (µ)ϕ ∗ j(υ) 1<br />
rµυ<br />
ϕ ∗ i (µ)ϕ ∗ j(υ) 1<br />
rµυ<br />
ϕ i(µ)ϕ j(υ)dτ µdτ(υ), <br />
ϕ j(µ)ϕ i(υ)dτ µdτ(υ). <br />
ϕ i <br />
δϕ i <br />
<br />
i<br />
δE = 2 <br />
δh(i) + <br />
(2δJij − δKij), <br />
δE = 2 <br />
<br />
(δϕ ∗ i ) hϕdϑ + <br />
<br />
(δϕ ∗ i )(2 Jj − <br />
Kj)ϕidϑ +<br />
+ 2 <br />
<br />
i<br />
i,j<br />
ϕ ∗ i h(δϕ)dϑ + <br />
<br />
i,j<br />
i<br />
i,j<br />
ϕ ∗ i (2 Jj − <br />
Kj)(δϕi)dϑ +<br />
(δϕ ∗ j)(2 Ji − <br />
Ki)ϕjdϑ ϕ ∗ j(2 Ji − <br />
Ki)(δϕj)dϑ .
δE = 2 <br />
<br />
i<br />
(δϕ ∗ i )<br />
<br />
<br />
h + (2 Jj − <br />
Kj) ϕidϑ j<br />
+ 2 <br />
<br />
<br />
(δϕi) ∗ h + (2 J ∗ j − K ∗ <br />
j )<br />
i<br />
j<br />
<br />
ϕ ∗ i dϑ. <br />
<br />
ϕi <br />
<br />
(δϕ ∗ i )ϕ jdϑ +<br />
<br />
(δϕ j)ϕ ∗ i dϑ = 0. <br />
E δE = 0 <br />
<br />
<br />
−2ɛji <br />
<br />
<br />
−2 <br />
ij<br />
−2 <br />
ij<br />
ɛji<br />
ɛji<br />
<br />
<br />
(δϕ ∗ i )ϕ jdϑ − 2 <br />
ij<br />
(δϕ ∗ i )ϕ jdϑ − 2 <br />
δE <br />
δE ′<br />
= 2 <br />
<br />
δE ′<br />
i<br />
(δϕ ∗ i )<br />
i<br />
ij<br />
ɛji<br />
ɛij<br />
<br />
<br />
h + (2 Jj − <br />
Kj) ϕi − <br />
j<br />
<br />
<br />
(δϕ j)ϕ ∗ i dϑ = 0 <br />
(δϕ i)ϕ ∗ jdϑ = 0 <br />
j<br />
ϕ jɛji<br />
+ 2 <br />
<br />
<br />
(δϕ ∗ i) h + (2 J ∗ j − K ∗ <br />
j ) ϕ ∗ i − <br />
= 0 <br />
<br />
<br />
h + (2 Jj − <br />
Kj) ϕi = <br />
j<br />
j<br />
j<br />
j<br />
<br />
dϑ<br />
ϕ ∗ jɛij<br />
<br />
dϑ. <br />
ϕ jɛji.
∗ h + (2 J ∗ j − K ∗ <br />
j )<br />
j<br />
ϕ ∗ i = <br />
ϕ ∗ jɛij<br />
j<br />
<br />
<br />
<br />
<br />
ϕ i <br />
j<br />
ϕ j(ɛji − ɛ ∗ ij) = 0, <br />
ɛji = ɛ ∗ ij. <br />
ɛ = [ɛ] <br />
<br />
F = h + G, <br />
F G <br />
<br />
<br />
<br />
(2 Jj − Kj). <br />
j<br />
F ϕ i = <br />
j<br />
ϕ jɛji, <br />
<br />
<br />
<br />
<br />
p <br />
χ <br />
ϕ i = <br />
p<br />
χ pCpi,
E ′<br />
[ϕ] = E[ϕ] + <br />
vinculos<br />
<br />
(−2εjiγ ij), <br />
γ ij = dϑ[(δϕ ∗ i )ϕ j − (δϕ j)ϕ ∗ i ] <br />
<br />
E[1,2, ...,n] = 2<br />
n<br />
i<br />
†<br />
ii +<br />
n<br />
i,j<br />
†<br />
i (2j − j)i, <br />
i = [cµi] j j <br />
h Jj Kj ϕ i <br />
δE = 2<br />
n<br />
i<br />
(δ †<br />
i )i +<br />
+ 2<br />
n<br />
i<br />
n<br />
i,j<br />
†<br />
i(δi) +<br />
<br />
(δ †<br />
i )(2j − j)i + (δ †<br />
j )(2i<br />
<br />
− i)j<br />
n<br />
i,j<br />
<br />
†<br />
i (2j − j)(δi) + †<br />
j (2i<br />
<br />
− i)(δj) . <br />
i j j j<br />
<br />
δE = 2 <br />
(δ †<br />
i<br />
i )<br />
<br />
+ <br />
<br />
(2j − j) i + 2 <br />
(δt <br />
i)<br />
j<br />
i<br />
∗ + <br />
j<br />
(2 ∗<br />
<br />
<br />
j − ∗<br />
j)<br />
<br />
i<br />
<br />
= + <br />
(2j − j), <br />
δE = 2 <br />
(δ †<br />
i<br />
j<br />
i )i + 2 <br />
(δ<br />
i<br />
t i)∗∗ i . <br />
<br />
<br />
†<br />
ij = δij,
Spq =<br />
<br />
<br />
χ ∗ pχ qdϑ. <br />
(δ †<br />
i )j + (δ t j) ∗ ∗ i = 0 <br />
−2ɛji <br />
−2 <br />
(δ †<br />
i )jɛij − 2 <br />
ij<br />
ij<br />
(δ t j) ∗ ∗ i ɛij = 0. <br />
δE ′<br />
= 0 <br />
[ɛij] <br />
<br />
()i = ɛii(i = 1, 2, .., n),
Spq =<br />
<br />
<br />
χ ∗ pχ qdϑ. <br />
(δ †<br />
i )j + (δ t j) ∗ ∗ i = 0 <br />
−2ɛji <br />
−2 <br />
(δ †<br />
i )jɛij − 2 <br />
ij<br />
ij<br />
(δ t j) ∗ ∗ i ɛij = 0. <br />
δE ′<br />
= 0 <br />
[ɛij] <br />
<br />
()i = ɛii(i = 1, 2, .., n),
Spq =<br />
<br />
<br />
χ ∗ pχ qdϑ. <br />
(δ †<br />
i )j + (δ t j) ∗ ∗ i = 0 <br />
−2ɛji <br />
−2 <br />
(δ †<br />
i )jɛij − 2 <br />
ij<br />
ij<br />
(δ t j) ∗ ∗ i ɛij = 0. <br />
δE ′<br />
= 0 <br />
[ɛij] <br />
<br />
()i = ɛii(i = 1, 2, .., n),
Spq =<br />
<br />
<br />
χ ∗ pχ qdϑ. <br />
(δ †<br />
i )j + (δ t j) ∗ ∗ i = 0 <br />
−2ɛji <br />
−2 <br />
(δ †<br />
i )jɛij − 2 <br />
ij<br />
ij<br />
(δ t j) ∗ ∗ i ɛij = 0. <br />
δE ′<br />
= 0 <br />
[ɛij] <br />
<br />
()i = ɛii(i = 1, 2, .., n),
Spq =<br />
<br />
<br />
χ ∗ pχ qdϑ. <br />
(δ †<br />
i )j + (δ t j) ∗ ∗ i = 0 <br />
−2ɛji <br />
−2 <br />
(δ †<br />
i )jɛij − 2 <br />
ij<br />
ij<br />
(δ t j) ∗ ∗ i ɛij = 0. <br />
δE ′<br />
= 0 <br />
[ɛij] <br />
<br />
()i = ɛii(i = 1, 2, .., n),