王昱喬-第四週作業

Use Spartan or WebMO to calculate the ionization energy of atoms with atomic number 1~10, by using CCSD(T)、MP4 and MP2 theoretical method with 6-31G* and 6-311+G(2df,2p) basis set, and do some simple statistical analysis

Data Link:Google Drive

1、ionization energy ( unit: kcal/mol )

H

He

Li

Be

B

C

N

O

F

Ne

CCSD(T)/6-31G*

312.6

550.0

122.9

212.0

179.8

249.0

328.9

298.8

386.2

483.8

MP2/6-31G*

312.6

547.7

122.9

199.4

182.4

252.2

332.6

298.5

387.6

487.4

MP4/6-31G*

312.6

549.9

122.9

209.2

180.8

250.2

330.3

298.9

386.4

484.3

experimental value

313.6

567.0

122.7

215.0

191.3

259.6

335.2

314.0

401.8

497.3

 

H

He

Li

Be

B

C

N

O

F

Ne

CCSD(T)/6-311+G(2df,2p)

313.6

563.3

123.1

214.1

188.9

257.6

333.6

308.3

396.8

493.6

MP2/6-311+G(2df,2p)

313.6

559.2

123.1

203.0

190.2

259.3

336.4

306.7

398.2

498.5

MP4/6-311+G(2df,2p)

313.6

563.2

123.1

211.4

189.9

258.8

334.9

308.2

397.1

494.4

experimental value

313.6

567.0

122.7

215.0

191.3

259.6

335.2

314.0

401.8

497.3

 

2、絕對誤差 ( unit: kcal/mol )

H

He

Li

Be

B

C

N

O

F

Ne

CCSD(T)/6-31G*

 0.9 17.0 0.2 2.9 11.6 10.6 6.3 15.2 15.6 13.5

MP2/6-31G*

 0.9 19.3 0.2 15.6 9.0 7.4 2.6 15.6 14.2 9.9

MP4/6-31G*

 0.9 17.1 0.2 5.8 10.5 9.4 4.9 15.1 15.3 13.0

CCSD(T)/6-311+G(2df,2p)

 0.1 3.7 0.4 0.9 2.4 2.0 1.5 5.7 4.9 3.7

MP2/6-311+G(2df,2p)

 0.1 7.8 0.4 11.9 1.1 0.3 1.2 7.3 3.5 1.2

MP4/6-311+G(2df,2p)

 0.1 3.8 0.4 3.6 1.4 0.8 0.3 5.8 4.7 2.9

 

Organize the calculated data of ionization energy, and compare it with the experimental value

1       2

3       4

5       6 

7       8 

 

  • Conclusion

以6-31G*為basis set時，三種方法的絕對平均誤差為MP2(9.5 kcal/mol) > CCSD(T)(9.4 kcal/mol) > MP4(9.2 kcal/mol)

以6-311+G(2df,2p)為basis set時，三種方法的絕對平均誤差為MP2(3.5 kcal/mol) > CCSD(T)(2.5 kcal/mol) > MP4(2.4 kcal/mol)