許慧霖-第十週作業

11

1

 

MP2
6-31+G(d,p)

Hartree

  

Hartree

  

Hartree

H2

-1.15766

H

-0.49823

H

-0.49823

Li2

-14.88597

Li

-7.43156

Li

-7.43156

B2

-49.05187

B

-24.56311

B

-24.56311

C2

-75.70118

C

-37.73661

C

-37.73661

N2

-109.26193

N

-54.45920

N

-54.45920

O2

-149.90884

O

-74.88529

O

-74.88529

F2

-199.05306

F

-99.49882

F

-99.49882

Si2

-577.82043

Si

-288.87286

Si

-288.87286

P2

-681.64479

P

-340.74774

P

-340.74774

S2

-795.21150

S

-397.55486

S

-397.55486

Cl2

-919.17502

Cl

-459.55409

Cl

-459.55409

MP2
6-31+G(d,p)

AE
kcal/mol

EXP.(De)
kcal/mol

誤差
kcal/mol

H2

101.2

109.5

8.3

Li2

14.3

24.6

10.3

B2

-46.6

67.1

113.8

C2

143.0

145.7

2.7

N2

215.6

228.5

12.9

O2

86.8

120.0

33.2

F2

34.8

38.2

3.4

Si2

46.9

75.0

28.1

P2

93.7

117.1

23.4

S2

63.9

101.7

37.8

Cl2

41.9

58.0

16.0

1 hartree = 627.5095 kcal/mol（資料來源：https://lab409chem.ccu.edu.tw/var/file/80/1080/img/866/qchem.pdf）

實驗值來源 (the Source of Experimental Values) : https://lab409chem.ccu.edu.tw/var/file/80/1080/img/866/AtomizationEnergies.pdf

11

1

 

B3LYP
aug-cc-pVTZ

Hartree

  

Hartree

  

Hartree

H2

-1.18002

H

-0.50226

H

-0.50226

Li2

-15.01741

Li

-7.49205

Li

-7.49205

B2

-49.39023

B

-24.66389

B

-24.66389

C2

-75.90814

C

-37.85906

C

-37.85906

N2

-109.57059

N

-54.50241

N

-54.50241

O2

-150.32336

O

-75.09418

O

-75.09418

F2

-199.59143

F

-99.76614

F

-99.76614

Si2

-578.88502

Si

-289.39677

Si

-289.39677

P2

-682.75429

P

-341.22607

P

-341.22607

S2

-796.40345

S

-398.13931

S

-398.13931

Cl2

-920.43675

Cl

-460.17533

Cl

-460.17533

B3LYP
aug-cc-pVTZ

AE
kcal/mol

EXP.(De)
kcal/mol

誤差
kcal/mol

H2

110.1

109.5

-0.7

Li2

20.9

24.6

3.7

B2

39.2

67.1

28.0

C2

119.2

145.7

26.5

N2

355.0

228.5

-126.6

O2

84.7

120.0

35.3

F2

37.1

38.2

1.1

Si2

57.4

75.0

17.6

P2

189.6

117.1

-72.5

S2

78.3

101.7

23.3

Cl2

54.0

58.0

4.0

 

1

1

−ΔH°f (H2O)

= TAEcalc (H2O) − [ TAEexpt(H2) + 1/2 TAEexpt(O2)]

= TAEB.O. (H2O) + 2 Ethermal (H) + Ethermal (O) − ZPE(H2O) − Ethermal (H2O) + 2 RT – [ 2 ΔH°f (H) + ΔH°f (O) ]

MP2
aug-cc-pVTZ

Hartree

  

Hartree

  

Hartree

AE
kcal/mol

H2

-1.16502

H

-0.49982

H

-0.49982

103.8

LiH

-8.01501

H

-0.49982

Li

-7.43271

51.8

BeH2

-15.83347

H

-0.49982

Be

-14.60119

146.0

BH3

-26.51501

H

-0.49982

B

-24.57658

275.5

CH4

-40.41446

H

-0.49982

C

-37.75956

411.4

NH3

-56.46054

H

-0.49982

N

-54.37872

365.4

H2O

-76.32899

H

-0.49982

O

-74.95929

232.2

HF

-100.34089

H

-0.49982

F

-99.61211

143.7

MP2
aug-cc-pVTZ

AHn
(ZPE+ Ethermal)
kcal/mol

RT
0.592 kcal/mol

ΔH°f (H)
kcal/mol

 ΔH°f (A )
kcal/mol

H2

7.9

2.368

52.1

52.1

LiH

3.5

2.368

52.1

38.1

BeH2

9.8

3.848

104.2

N/A

BH3

18.6

5.328

156.3

135.0

CH4

30.3

6.808

208.4

171.3

NH3

23.5

5.328

156.3

113.0

H2O

15.2

3.848

104.2

59.6

HF

7.4

2.368

52.1

19.0

H2O = (232.2-(15.2) +3.848-(104.2+59.6))*(-1)=57.1

MP2
aug-cc-pVTZ

−ΔH°f

ΔH°f

EXP.(De)
kcal/mol

誤差
kcal/mol

H2

-6.0

6.0

0.0

-6.0

LiH

-39.5

39.5

33.6

-5.9

BeH2

N/A

N/A

N/A

N/A

BH3

-29.1

29.1

21.0

-8.1

CH4

8.2

-8.2

-17.8

-9.6

NH3

78.0

-78.0

-11.0

67.0

H2O

57.1

-57.1

-57.8

-0.7

HF

67.6

-67.6

-65.3

2.3

1 hartree = 627.5095 kcal/mol（資料來源：https://lab409chem.ccu.edu.tw/var/file/80/1080/img/866/qchem.pdf）

實驗值來源 (the Source of Experimental Values) : https://cccbdb.nist.gov/xp1x.asp?prop=8

CCSD(T)
aug-cc-pVTZ

Hartree

  

Hartree

  

Hartree

AE
kcal/mol

H2

-1.17262

H

-0.49982

H

-0.4998212

108.5

LiH

-8.02320

H

-0.49982

Li

-7.43271

56.9

BeH2

-15.84929

H

-0.49982

Be

-14.618456

145.1

BH3

-26.53906

H

-0.49982

B

-24.598451

276.8

CH4

-40.44089

H

-0.49982

C

-37.781825

414.0

NH3

-56.48055

H

-0.49982

N

-54.417503

353.7

H2O

-76.34233

H

-0.49982

O

-74.978952

228.2

HF

-100.34958

H

-0.49982

F

-99.627827

139.3

CCSD(T)
aug-cc-pVTZ

AHn
(ZPE+ Ethermal)
kcal/mol

RT
0.592 kcal/mol

ΔH°f (H)
kcal/mol

 ΔH°f (A )
kcal/mol

H2

7.9

2.368

52.1

52.1

LiH

3.5

2.368

52.1

38.1

BeH2

N/A

3.848

104.2

N/A

BH3

18.4

5.328

156.3

135.0

CH4

30.1

6.808

208.4

171.3

NH3

23.4

5.328

156.3

113.0

H2O

15.2

3.848

104.2

59.6

HF

7.4

2.368

52.1

19.0

CCSD(T)
aug-cc-pVTZ

−ΔH°f

ΔH°f

EXP.(De)
kcal/mol

誤差
kcal/mol

H2

-1.2

1.2

0.0

-1.2

LiH

-34.4

34.4

33.6

-0.8

BeH2

N/A

N/A

N/A

N/A

BH3

-27.6

27.6

21.0

-6.6

CH4

11.1

-11.1

-17.8

-6.8

NH3

66.3

-66.3

-11.0

55.3

H2O

53.1

-53.1

-57.8

-4.7

HF

7.4

2.368

52.1

-2.1

 

1

1