Valence_bonding

1

r12

2

ˆ

1

2

1

2

1

1

1

1

H(1,2)

2

1

2

2

r

(1)

rA1

rA2

rB2

rB1

B

rA (1)

rB(2)

1

1

r12

RAB

rA (2)

ˆ

1

2

1

ˆ

1

2

1

RAB

hA1(1)

2

1

r

; hB2(2)

2

2

r

A1

B2

A

B

I(1,2) 1sA 1 1sB 2

II(1,2) 1sA 2 1sB 1

e(1) e(2) !!!

S (1,2) I II

(1,2)

I

II

A

S (1,2) S (2,1)

A (1,2) A (2,1)

(1,2)

(1,2) S

A

(1,2)

(1,2)

(1,2) S (1,2)

S

S

A

A

S

S

1

1) 2);

S

1

1

1) 2)

1) 2)

0

SS SS0

SA

(1,2)

2

2

(1) (2)

(2) (1)

S

1

1) 2),

S

Синглет

Триплет

E ES,A

ˆ

(1,2)dV1dV2

S,A

(1,2)H(1,2) S,A

E

E

1

Q P

S ,A

1 S2

Q 2C K

1

P 2 S A

S2

R

R

C

A

1

2

dV1

1s

A

2

2

1s

1

2

1s

2

2

dV2 0

1s

dV2

B

dV1

B

rB

(1)

rB (2)

rA (1)

rA

(2)

1sA (1) 1sB(1)

dV1

1sA (1) 1sB(1)

dV1 ... 0

rA (1)

rB(1)

K

1

2

1s

2

2

dV1dV2 0

1s

A

B

r1,2

A

1sA 1 1sB 2 1sA 2 1sB 1

dV1dV2 0

r1,2

C

K

A

S

Q

P

-0,47255

-0,406

0,42595

0,18415

0,5865

-0,01915

-0,12015

-0,5837

-0,55785

0,49035

0,29685

0,7252

-0,0104

-0,16165

R 1,5

0,13915

E (R

2)

1

0,1035

Q '

P '

1

1,344

1,1035

E (R 1,5) 1

0,17205

1 0,112752 1,1128

6

Q '

P '

1,5259

2EH

1

1

2

2

D ED 2EH (E E0 ) 1 ( 1,1128

h 0

)

a.o.e.

2

0,1128 0,0099277

kJ

1 4,359814 10 18 6,022 1023

2625,48

mol

296 26 322

kJ

mol

Dexperimental or E experimental

436

kJ

D

mol

E

D

/Eexperimental 0,74

D

E experimental E

114

kJ

(!) 0,04342 Hartree(a.o.e.)

D

D

mol