H 2 /0.736ÅG03NWChemGAMESS cc-pVTZHF-1.13299-1.13301 MP2-1.16465-1.16479 cc-pVQZHF-1.13349-1.13350 MP2-1.16659-1.16666 cc-pV5ZHF-1.13364-1.13365 MP2-1.16728-1.16737-1.16721

G03,NWCHEM 에서 BASIS SET 사용하기(CARTESIAN & SPHERICAL)

H2/0.736Å G03 NWChem

GAMESS

cc-pVTZ HF -1.13299 -1.13301 -1.13301

MP2 -1.16465 -1.16479 -1.16479

cc-pVQZ HF -1.13349 -1.13350 -1.13350

MP2 -1.16659 -1.16666 -1.16666

cc-pV5Z HF -1.13364 -1.13365 -1.13365

MP2 -1.16728 -1.16737 -1.16721

Cc-pVXZ

Method Program a b c

HFGauss-

ian-

1.133704286

0.02645502646

1.203972804

NWChem

-1.13371617

6

0.02461657943

1.183770097

GAMESS -1.13371617

6

0.0246165794

3

1.183770097

exp( ) scfE a b cX to the cc-pVXZ results on data points for3 5X

Program a b

Gaussian -0.03420655738

0.07081967214

NWChem -0.03430754098

0.07344262296

GAMESS -0.03397967213

0.05245901640

3 corrE a bX to the cc-pVXZ results, based on data points for 3 5X

Basis-set Convergence & complete Basis Limit

[Question] 어느 정도로 높은 Basis set 을 사용해야 할까 ?

<Answer-1>

HF, DFT 는 basis set size 에 대해서 지수적으로 수렴한다 .

Dunning basis set (cc-pVXZ) 을 쓰면 총에너지는 e-cx 로 수렴한다 .

그다지 높지 않은 Basis set 을 써도 된다 .

<Answer-2>

Correlated 계산 (MPn,CCSD, …) 는 Basis set size 에 대한 수렴성이 느리다 .

Dunning basis set 을 쓸 경우 1/x3 로 수렴한다고 알려져 있다 .

매우 높은 Basis set 을 써야 한다 .

왜 그럴까 ?

J.Chem.Phys. 106, 9639, (1997)

J.Chem.Phys. 100, 7410, (1994)

exp( ) scfE a b cX 3 corrE a bX

NWChem 과 GAMESS 의SCF energy가 같다 .

O2/triplet/1.15Å G03 NWChem GAMESS

cc-pVTZ HF -149.6805

3

-149.6805

3

-149.68053

MP2 -150.1376

9

-150.1376

9

-150.13769

cc-pVQZ HF -149.6924

8

-149.6924

8

-149.69248

MP2 -150.2260

6

-150.2260

6

-150.22606

cc-pV5Z HF -149.6954

5

-149.6954

5

-149.69541

MP2 -150.2624

7

-150.2624

7

-150.25672


HFGauss-

ian-

149.69643231.035842776 1.392169326

NWChem

-149.6963793

1.064321277 1.402321697

GAMESS -149.6963618

1.074063920 1.405728855


Program a b

Gaussian -0.6021045902 4.385573771

NWChem -0.6017767213 4.364590164

GAMESS -0.5904037705 3.636721312



SCF 에너지가 거의 다 같다 .

Ca/singlet G03 NWChem GAMESS

cc-pVTZ HF -676.75794 -676.75794 -676.75794

MP2 -676.95065 -676.95065 -676.95065

cc-pVQZ HF -676.75814 -676.75814 -676.75814

MP2 -677.00460 -677.00460 -677.00460

cc-pV5Z HF -676.75817 -676.75817 -676.75817

MP2 -677.05037

-677.05037

-677.05010

G03 과 GAMESS의 Ca cc-pV(T,Q)Z 의 Exponent 는 같으나coefficient 가 다르다 .

GAMESS 는 Ca cc-pV5Z 이상은 g function 까지만 계산h 이상은 뺀다 .

G03 과 Nwchem 의 Basis set 은 모두 같다 .


HFGauss-

ian-

676.7581753

0.06971677560

1.897119985

NWChem

GAMESS


Program a b

Gaussian -0.3401895082 5.998688525

NWChem

GAMESS


NWChem, GAMESS 는 Cartesian Basis function 이 디폴트Gaussian 은 spherical 이 default

exp( ) scfE a b cX


Cartesian Basis Functions

Spherical Basis Functions

P 3 3

D 6 5

F 10 7

G 15 9

H 21 11

,l n mF x y z l n m L 2 1F L

NWChem input : Linearly dependent orbital 을 처리하는 option

Cartesian Basis Function Spherical Basis Function

NWChem output

Cartesian Basis Function Spherical Basis Function

Gaussian input

Cartesian Basis Function

Spherical Basis Function

Gaussian output

Cartesian Basis Function

Spherical Basis Function

G03,NWCHEM 에서 BASIS SET 사용하기( 응용 )

G03 – BASIS SET

Basis Set Applies to Polarization Functions Diffuse Functions

STO-3G H-Xe *

3-21G H-Xe * or ** +

6-21G H-Cl (d)

4-31G H-Ne (d) or (d,p)

6-31G H-Kr (3df,3pd) ++

6-311G H-Kr (3df,3pd) ++

D95 H-Cl except Na and Mg (3df,3pd) ++

D95V H-Ne (d) or (d,p) ++

SHC H-Cl *

CEP-4G H-Rn * (Li-Ar only)



G03 – BASIS SET

Atoms cc-pVDZ cc-pVTZ cc-pVQZ cc-pV5Z cc-pV6Z

H 2s,1p 3s,2p,1d 4s,3p,2d,1f 5s,4p,3d,2f,1g 6s,5p,4d,3f,2g,1h

He 2s,1p 3s,2p,1d 4s,3p,2d,1f 5s,4p,3d,2f,1g not available

B-Ne 3s,2p,1d 4s,3p,2d,1f 5s,4p,3d,2f,1g 6s,5p,4d,3f,2g,1h 7s,6p,5d,4f,3g,2h,1i

Al-Ar 4s,3p,1d 5s,4p,2d,1f 6s,5p,3d,2f,1g 7s,6p,4d,3f,2g,1h not available

Ga-Kr 5s,4p,1d 6s,5p,3d,1f not available not available not available

1. Basis set 을 고르고2. atom 을 고른 뒤

3. format 을 정하고 4. Click!

G03 – BASIS SEThttp://bse.pnl.gov

http://bse.pnl.gov/

여기서부터 사용

#p UMP2(full)/Gen SCF=tight test 1,220 0.000000 0.000000 0.0000001 0.384468 2.230406 0.0000001 -0.384468 2.230406 0.0000001 -2.230406 0.384468 0.0000001 -2.230406 -0.384468 0.0000001 -0.384468 -2.230406 0.0000001 0.384468 -2.230406 0.0000001 2.230406 -0.384468 0.0000001 2.230406 0.384468 0.000000

H 0cc-pVQZ****Ca 0 S 19 1.00 7503960.0000000 0.00000224 1123486.0000000 0.00001744 255663.5000000 0.00009177 72416.0600000 0.00038768

…… G 1 1.00 0.1466000 1.0000000****

Basis set 자리에 Gen 이라 입력

basis set 은 직접 입력도 가능하고 (ex. Ca),기존의 basis set 을 집어 넣어도 된다 (ex. H).basis 의 끝은 **** 로 마무리

G03 – BASIS SET

NWCHEM – BASIS SET

http://www.emsl.pnl.gov/capabilities/computing/nwchem/docs/usermanual.pdf

위 사이트에서 Standard Basis Sets 참조

http://www.emsl.pnl.gov/capabilities/computing/nwchem/docs/usermanual.pdf

1. Basis set 을 고르고2. atom 을 고른 뒤

3. format 을 정하고 4. Click!

NWCHEM – BASIS SEThttp://bse.pnl.gov

http://bse.pnl.gov/

여기서부터 사용

Nwchem 은 basis/libraries 디렉토리 아래 해당하는 basis 이름의 파일에 직접 입력해서 사용한다 .




G03,NWCHEM 에서 DFT 사용하기( 응용 )

G03 – DFT

%mem=3000mb#p cc-pVTZ IOp(3/74=1000) SCF=tight

PBE-EXonly(cc-pVTZ)

0,120 0.0000000 0.0000000 0.00000001 0.0000000 0.0000000 2.70000001 0.7991830 0.000000000 2.57901301 2.7000000 0.0000000 0.00000001 2.5790130 0.0000000 -0.79918301 0.0000000 0.0000000 -2.70000001 -0.7991830 0.0000000 -2.57901301 -2.7000000 0.0000000 0.00000001 -2.5790130 0.0000000 0.7991830

#p PBEPBE/cc-pVTZ ↓#p cc-pVTZ IOp(3/74=1000)

http://www.gaussian.com/g_tech/g_iops/ov3.htm#3-74

NWCHEM – DFT

…..

DFT xc xpbe96 cpbe96 MULT 2 ITERATIONS 3000 CONVERGENCE energy 1.0e-6 convergence gradient 5e-4 SMEAR 0.001END

….자세한 사용법은 Nwchem man-ualChap. 11 장 참조

G03/Iop=200 E= -1.04375634358 Ha G03/Iop=205 E= -1.17295958614 Ha

NWChem/Slater E= -1.043763525494 Ha

G03 에서 Slater Exchange 는 Iop=200 이다 .

G03/Iop=300 E= -1.07137561396 Ha

http://www.gaussian.com/g_tech/g_iops/ov3.htm

Documents

H 2 /0.736ÅG03NWChemGAMESS cc-pVTZHF-1.13299-1.13301 MP2-1.16465-1.16479 cc-pVQZHF-1.13349-1.13350 MP2-1.16659-1.16666 cc-pV5ZHF-1.13364-1.13365 MP2-1.16728-1.16737-1.16721