•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. The unit of the ionization energy is kcal/mol .
•Organize the calculated data of ionization energy, and compare it with the experimental value, then present the result on your exercise page.
實驗值資料來源:https://cccbdb.nist.gov/xp1x.asp?prop=8
|
MP2 |
|
MP4 |
|
CCSD(T) |
|
|
|
(atom) |
6-31 |
6-311+G(2df,2p) |
6-31 |
6-311+G(2df,2p) |
6-31 |
6-311+G(2df,2p) |
|
H |
-0.4982329 |
-0.4998098 |
-0.4982329 |
-0.4998098 |
-0.4982329 |
-0.49981 |
|
He |
-2.870162 |
-2.895778 |
-2.869939 |
-2.895581 |
-2.870162 |
-2.895778 |
|
Li |
-7.431858 |
-7.445008 |
-7.431879 |
-7.447268 |
-7.431882 |
-7.447348 |
|
Be |
-14.5932603 |
-14.5997423 |
-14.6088756 |
-14.6130566 |
-14.6134355 |
-14.617343 |
|
B |
-24.558719 |
-24.5746805 |
-24.5759443 |
-24.5927867 |
-24.579675 |
-24.5966991 |
|
C |
-37.732974 |
-37.7560353 |
-37.7504338 |
-37.7756905 |
-37.752739 |
-37.778409 |
|
N |
-54.4570079 |
-54.4929866 |
-54.4732564 |
-54.5104177 |
-54.4738048 |
-54.511331 |
|
O |
-74.880037 |
-74.9500366 |
-74.895973 |
-74.9684261 |
-74.896637 |
-74.9693919 |
|
F |
-99.487271 |
-99.5985612 |
-99.4986523 |
-99.6134355 |
-99.498886 |
-99.613816 |
|
Ne |
-128.6247223 |
-128.7873008 |
-128.6292144 |
-128.7945248 |
-128.6285534 |
-128.793599 |
|
|
MP2 |
|
MP4 |
|
CCSD(T) |
|
|
(catiom) |
6-31 |
6-311 |
6-31 |
6-311 |
6-31 |
6-311 |
|
H |
|
|
|
|
|
|
|
He |
-1.9936178 |
-1.9981392 |
-1.9936178 |
-1.9981392 |
-1.9936178 |
-1.9981 |
|
Li |
-7.2355365 |
-7.2358396 |
-7.2355365 |
-7.2358396 |
-7.235536 |
-7.2358396 |
|
Be |
-14.2755223 |
-14.2762037 |
-14.2755223 |
-14.2762037 |
-14.2755223 |
-14.276204 |
|
B |
-24.2680508 |
-24.2715217 |
-24.2877879 |
-24.290122 |
-24.2932138 |
-24.295664 |
|
C |
-37.331066 |
-37.3427645 |
-37.3517246 |
-37.3632594 |
-37.355965 |
-37.367819 |
|
N |
-53.926986 |
-53.9569563 |
-53.9468995 |
-53.9767613 |
-53.9496761 |
-53.9796902 |
|
O |
-74.4044033 |
-74.4612986 |
-74.419222 |
-74.4772537 |
-74.4203973 |
-74.4780129 |
|
F |
-98.869629 |
-98.9639451 |
-98.8828401 |
-98.9806343 |
-98.8834981 |
-98.9813416 |
|
Ne |
-127.848065 |
-127.9928527 |
-127.857446 |
-128.0066089 |
-127.8575601 |
-128.0069661 |
|
|
MP2 |
|
MP4 |
|
CCSD(T) |
|
|
|
|
6-31 |
6-311 |
6-31 |
6-311 |
6-31 |
6-311 |
EXP |
|
H |
312.6 |
313.6 |
312.6 |
313.6 |
312.6 |
313.6 |
313.6 |
|
He |
550.0 |
563.3 |
549.9 |
563.2 |
550.0 |
563.3 |
567.0 |
|
Li |
123.2 |
131.3 |
123.2 |
132.7 |
123.2 |
132.7 |
124.3 |
|
Be |
199.4 |
203.0 |
209.2 |
211.4 |
212.0 |
214.1 |
215.0 |
|
B |
182.4 |
190.2 |
180.8 |
189.9 |
179.8 |
188.9 |
191.4 |
|
C |
252.2 |
259.3 |
250.2 |
258.8 |
249.0 |
257.6 |
259.7 |
|
N |
332.6 |
336.4 |
330.3 |
334.9 |
328.9 |
333.6 |
335.2 |
|
O |
298.5 |
306.7 |
299.2 |
308.2 |
298.8 |
308.3 |
314.0 |
|
F |
387.6 |
398.2 |
386.4 |
397.1 |
386.2 |
396.9 |
401.8 |
|
Ne |
487.4 |
498.5 |
484.3 |
494.4 |
483.8 |
493.6 |
497.3 |
| absolute | MP2 | MP4 | CCSD(T) | |||
| error | 6-31 | 6-311 | 6-31 | 6-311 | 6-31 | 6-311 |
| H | 0.9 | 0 | 0.9 | 0 | 0.9 | 0 |
| He | 17 | 3.7 | 17.1 | 3.9 | 17 | 3.7 |
| Li | 1.1 | 6.9 | 1.1 | 8.3 | 1.1 | 8.4 |
| Be | 15.6 | 12 | 5.8 | 3.6 | 2.9 | 0.9 |
| B | 9 | 1.1 | 10.5 | 1.4 | 11.6 | 2.5 |
| C | 7.5 | 0.3 | 9.5 | 0.9 | 10.7 | 2 |
| N | 2.6 | 1.2 | 4.9 | 0.3 | 6.3 | 1.6 |
| O | 15.6 | 7.4 | 14.9 | 5.8 | 15.2 | 5.7 |
| F | 14.2 | 3.6 | 15.4 | 4.7 | 15.6 | 4.9 |
| Ne | 9.9 | 1.2 | 13 | 2.9 | 13.5 | 3.7 |
| mue | 10.4 | 4.2 | 10.3 | 3.5 | 10.4 | 3.7 |
以6-31G*為basis set時，三種方法的絕對平均誤差為MP2(10.4kcal/mol) = CCSD(T)(10.4 kcal/mol) > MP4(10.3 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(4.2 kcal/mol) > CCSD(T)(3.7 kcal/mol) > MP4(3.5kcal/mol)
以更換Basis set來說，每個理論方法皆有明顯的下降，MP2/CCSD使用6-311+G(2df,2p)的誤差差不多小。