molpro a quantum chemistry package adem tekin yrd. doc. dr. 15.06.2012 istanbul

MOLPROA quantum chemistry package

Adem TekinYrd. Doc. Dr.

15.06.2012 Istanbul

Turbomole 15.06.2012

Outline

— Introduction

— Input structure and introductory examples

— Brief introduction to SCS-MP2 and DFT-SAPT

— Applications of SAPT: Acetylene-Benzene dimer

— Towards the AcnBzn aggregates

— Exercise: Calculation of interaction energies for water dimer at MP2, SCS-MP2, B3LYP-D, DFT-SAPT (PBE0AC), DFT-SAPT (LPBE0AC) and CCSD(T) levels


Molpro

— Developed by H. –J. Werner (University of Stuttgart) and P. J. Knowles (Cardiff University)

— for more information please visit to:

— http://www.molpro.net

— A user mailing list is available under http://www.molpro.net/mailman/listinfo/molpro-user/?portal= user&choice=User+mailing+list

— In molpro, the emphasis is given to highly accurate computations, with extensive treatment of the electron correlation problem through the multiconfiguration-reference CI and coupled cluster methods.

http://www.molpro.net/mailman/listinfo/molpro-user/?portal


Running molpro— Molpro is accessed using the molpro command. The syntax is:

molpro [options] [datafile]

— datafile is the input. Prepare your input with .com extension.

— output will be written to a datafile.out file

— -d dir1:dir2:… where dir1:dir2:… is a list of directories which may be used for creating scratch files.

— There are more options…

— Molpro can be run in parallel:

-n specifies the number of cpu

-N specifies the number of tasks on the node


Submitting molpro jobs on UHEM

#!/bin/bash#BSUB -m karadeniz_temp1#BSUB -a intelmpi # bu kismi degistirmeyin !!!#BSUB -J triazine_avtz16 #isinizi tanimlayacak bir isim#BSUB -o triazine_avtz16.out # bu kismi degistirmeyin !!!#BSUB -e triazine_avtz16.err # bu kismi degistirmeyin !!!#BSUB -q workshop #kuyruk ismi#BSUB -n 16 # kullanilacak olan islemci sayisi#BSUB –P workshop#BSUB -R "span[ptile=8]" # bu kismi degistirmeyin !!!

echo 'Starting time:'datemolpro -n 16 -N 8 --no-xml-output $PWD/triazine_avtz16.com>triazine_avtz16.logecho 'Ending time:'date


Molpro input structure***,title !title (optional)memory,4,m !memory specification (optional)file,1,name.int !permanent named integral file (optional)file,2,name.wfu !permanent named wavefunction file (optional)gprint,options !global print options (optional)gthresh,options !global thresholds (optional)gdirect[,options] !global direct (optional)gexpec,opnames !global definition of one-electron operators (optional)basis=basisname !basis specification. If not present, cc-pVDZ !is default geometry={...} !geometry specificationvar1=value,var2=value,... !setting variables for geometry and/or wavefunction {command,options !program or procedure namedirective,data,option !directives for command (optional)...} !end of command block--- !end of input (optional)

Molpro input examples (http://www.be.itu.edu.tr/~adem.tekin/molpro)

TURBOMOLE usage philosophy! SCF calcultion for water. (ex1.com)

***,h2o !A titler=1.85,theta=104 !set geometry parametersgeometry={O; !z-matrix geometry input H1,O,r; H2,O,r,H1,theta}hf !closed-shell scf

The default basis is cc-pVDZ abbreviated as VDZ

! SCF calculation for water using vtz (ex2.com)

***,h2o cc-pVTZ basis !A titler=1.85,theta=104 !set geometry parametersgeometry={O; !z-matrix geometry input H1,O,r; H2,O,r,H1,theta}basis=VTZ !use VTZ basishf !closed-shell scf


Molpro input examples (http://www.be.itu.edu.tr/~adem.tekin/molpro)

:%s/water-ccsdt-avdz/ex1/g


Molpro examples! Geometry optimization at the HF level for water (ex3.com)

***,h2o !A titler=1.85,theta=104 !set geometry parametersgeometry={O; !z-matrix geometry input H1,O,r; H2,O,r,H1,theta}basis=6-31g** !use Pople basis sethf !closed-shell scfoptg !do scf geometry optimization

! Single point CCSD(T) for water (ex4.com)

***,h2o !A titler=1.85,theta=104 !set geometry parametersgeometry={O; !z-matrix geometry input H1,O,r; H2,O,r,H1,theta}basis=VTZ !use VTZ basishf !closed-shell scfccsd(t) !do ccsd(t) calculation


Electron correlation methods

— Hartree-Fock is a single determinant wave function method where molecular orbitals are varied.

— Configuration Interaction (CI) is a multiple determinant wavefunction method where molecular orbitals are not varied.

— CI wavefunction is constructed by starting with the HF wavefunction and making new determinants by promoting electrons from the occupied to unoccupied orbitals.

— Depending on the number of excitations used to make the determinants, CI methods are called CIS, CISD, CISDT, CISDTQ and full CI.

— Multi-configurational self-consistent field (MCSCF) calculations also use multiple determinants. In contrast to the CI, orbitals are also optimized.

— An MCSCF calculation in which all combinations of the active space orbitals are included is called a complete active space self-consistent field (CASSCF) calculation.


Electron correlation methods

— In a CASSCF wavefunction the occupied orbital space is divided into a set of inactive or closed-shell orbitals and a set of active orbitals. All inactive orbitals are doubly occupied in each Slater determinant. On the other hand, the active orbitals have varying occupations, and all possible Slater determinants (or CSFs) are taken into account which can be generated by distributing the Nact=Nel-2mclosed electrons in all possible ways among the active orbitals, where mclosed is the number of closed-shell (inactive) orbitals, and Nel is the total number of electrons.

— It is possible to construct a CI wavefunction starting with an MCSCF calculation rather than starting with a HF wavefunction. This starting wavefunction is called the reference state. These calculations are called multi-reference configuration interaction (MRCI).

— Coupled cluster (CC) calculations are similar to CI calculations in that the wavefunction is a linear combination of many determinants. The means for choosing the determinants in CC is more complex than CI. There are variants of CC: CCSD, CCSDT and CCSD(T).


Molpro examples

! Geometry optimization at the HF level for water (ex5.com)

***,h2o !A titler=1.85,theta=104 !set geometry parametersgeometry={o; !z-matrix geometry input h1,O,r; h2,O,r,H1,theta}basis=vtz !use VTZ basishf !closed-shell scfccsd(t) !do ccsd(t) calculationcasscf !do casscf calculationmrci !do mrci calculation

Molpro example – tables ! Put the results into a table (ex6.com)

***,h2o !A titler=1.85,theta=104 !set geometry parametersgeometry={o; !z-matrix geometry input h1,O,r; h2,O,r,H1,theta}basis=vtz !use VTZ basishf !closed-shell scfe(1)=energy !save scf energy in variable e(1)method(1)=program !save the string ’HF’ in variable method(1)ccsd(t) !do ccsd(t) calculatione(2)=energy !save ccsd(t) energy in variable e(2)method(2)=program !save the string ’CCSD(T)’ in variable method(2)casscf !do casscf calculatione(3)=energy !save scf energy in variable e(3)method(3)=program !save the string ’CASSCF’ in variable method(3)mrci !do mrci calculatione(4)=energy !save scf energy in variable e(4)method(4)=program !save the string ’MRCI’ in variable method(4)table,method,e !print a table with resultstitle,Results for H2O, basis=$basis !title for the table

Molpro example – Procedures (ex7.com)

***,h2o !A titleproc save_e !define procedure save_eif(#i.eq.0) i=0 !initialize variable i if it does not existi=i+1 !increment ie(i)=energy !save scf energy in variable e(i)method(i)=program !save the present method in variable method(i)endproc !end of procedure

r=1.85,theta=104 !set geometry parametersgeometry={o; !z-matrix geometry input h1,O,r; h2,O,r,H1,theta}basis=vtz !use VTZ basishf !closed-shell scfsave_e !call procedure, save resultsccsd(t) !do ccsd(t) calculationsave_e !call procedure, save resultscasscf !do casscf calculationsave_e !call procedure, save resultsmrci !do mrci calculationsave_e !call procedure, save resultstable,method,e !print a table with resultstitle,Results for H2O, basis=$basis !title for the table

Molpro example – do loops (ex8.com)***,H2O potential

symmetry,x !use cs symmetrygeometry={o; !z-matrixh1,o,r1(i);h2,o,r2(i),h1,theta(i) }basis=vdz !define basis setangles=[100,104,110] !list of anglesdistances=[1.6,1.7,1.8,1.9,2.0] !list of distancesi=0 !initialize a counterdo ith=1,#angles !loop over all angles H1-O-H2do ir1=1,#distances !loop over distances for O-H1do ir2=1,ir1 !loop over O-H2 distances(r1.ge.r2)i=i+1 !increment counterr1(i)=distances(ir1) !save r1 for this geometryr2(i)=distances(ir2) !save r2 for this geometrytheta(i)=angles(ith) !save theta for this geometryhf; !do SCF calculationescf(i)=energy !save scf energy for this geometryccsd(t); !do CCSD(T) calculationeccsd(i)=energc !save CCSD energyeccsdt(i)=energy !save CCSD(T) energyenddo !end of do loop ithenddo !end of do loop ir1enddo !end of do loop ir2{table,r1,r2,theta,escf,eccsd,eccsdt !produce a table with resultshead, r1,r2,theta,scf,ccsd,ccsd(t) !modify column headers for tablesave,h2o.tab !save the table in file h2o.tabtitle,Results for H2O, basis $basis !title for tablesort,3,1,2} !sort table


Program control— ***,text ! Starting a job

— --- ! Ending a job

— MEMORY,n,scale; ! Allocating dynamic memory

— MEMORY,90000 ! allocates 90 000 words of memory— MEMORY,500,K ! allocates 500 000 words of memory— MEMORY,2,M !allocates 2 000 000 words of memory— 1 word = 8 bytes

— IF($method.eq.’HF’) then ... ENDIF

— GTHRESH,key1=value1,key2=value2,. . . ! Global thresholds

— ENERGY ! Convergence threshold for energy (default 1.d-6)— ORBITAL ! Convergence threshold for orbital optimization in the SCF program (default 1.d-5).— gthresh,energy=1d-8,orbital=1d-7

Molpro example – Expectation values – dipole and quadrupole moments (ex9.com)

***,h2o propertiesgeometry={o;h1,o,r;h2,o,r,h1,theta} !Z-matrix geometry inputr=1 ang !bond lengththeta=104 !bond anglegexpec,dm,sm,qm compute dipole and quarupole moments$methods=[hf,multi,ci] !do hf, casscf, mrcido i=1,#methods !loop over methods$methods(i) !run energy calculatione(i)=energydip(i)=dmz !save dipole moment in variable dipquadxx(i)=qmxx !save quadrupole momemtsquadyy(i)=qmyyquadzz(i)=qmzzsmxx(i)=xx !save second momemtssmyy(i)=yysmzz(i)=zzenddotable,methods,dip,smxx,smyy,smzz !print table of first and second momentstable,methods,e,quadxx,quadyy,quadzz !print table of quadrupole moments


Geometry specification – using xyz coordinates

geomtyp=xyzgeometry={3 ! number of atomsThis is an example of geometry input for water with an XYZ fileO ,0.0000000000,0.0000000000,-0.1302052882H ,1.4891244004,0.0000000000, 1.0332262019H,-1.4891244004,0.0000000000, 1.0332262019}hf


Basis set

— BASIS,DEFAULT=VTZ,O=AVTZ,H=VDZ

— BASIS=VTZ,O=AVTZ,H=VDZ

— BASIS DEFAULT=VTZ O=AVTZ H=VDZ END


Density fitting

— Density fitting can be used to approximate the integrals in spin restricted Hartree-Fock (HF), density functional theory (KS), second-order Møller-Plesset perturbation theory (MP2 and RMP2), explicitly correlated MP2 (MP2-F12), and all levels of closed-shell local correlation methods (LCC2, LMP2-LMP4, LQCISD(T), LCCSD(T)).

— Density fitting is invoked by adding the prefix DF- to the command name, e.g. DF-HF, DF-KS, DF-MP2 and so on.

— Symmetry is not implemented for density fitting programs.

— By default, a fitting basis set will be chosen automatically that corresponds to the current orbital basis set and is appropriate for the method. For instance, if the orbital basis set is VTZ, the default fitting basis is VTZ/JKFIT for DF-HF or DF-KS, and VTZ/MP2FIT for DF-MP2.

— Examples:

BASIS=VTZ !use VTZ orbital basis DF-HF,DF_BASIS=VQZ !use VQZ/JKFIT fitting basis DF-MP2,DF_BASIS=VQZ !use VQZ/MP2FIT fitting basis


Calculating the intermolecular interactions in water dimer

— MP2

— SCS-MP2

— B3LYP-D

— DFT-SAPT

— CCSD(T)

Turbomole

Spin component scaled (SCS) MP2

S. Grimme, J. Chem. Phys., 2003, 118, 9095.

— SCS-MP2 is based on a separate scaling of the second-order parallel(αα+ββ) and antiparallel-spin (αβ) pair correlation energies e(2).

— The SCS-MP2 approximation to the correlation energy Ecorr is given by

— Here, pT and pS are empirical parameters determined to be 1/3 and 6/5.

— If you perform an MP2 calculation, you already have the SCS-MP2 energy.

Turbomole

The iterative formulation of Rayleigh-Schrödinger perturbation theory

Turbomole

Intermolecular perturbation theory

, ,


Symmetry adapted perturbation theory

• Contributions of third and higher orders :

• The total interaction energy :


A more simple way to calculate intermolecular interaction energy

• Supermolecular approach (SMA)

• Basis set superposition error (BSSE)

• Employ Counterpoise (CP) technique to avoid BSSE in SMA

• SAPT does not contain BSSE


The analysis of different types of intermolecular interactions


Applications of SAPT: Acetylene - Benzene

-10.8

-2.9

-5.8

T

S

SS

Turbomole

Comparison of SAPT with supermolecular calculations: Acetylene - Benzene

Aug-cc-pVTZ


Comparison of SAPT with supermolecular calculations: Acetylene - Furan

Aug-cc-pVTZ


The intermolecular PES: extrapolation to the cbs limit for Acetylene - Benzene

3 3

3 3

( ) ( 1) ( 1)( 1, ) with ( : 2, : 3, : 4...)

( 1)

corr corrcorr X E X X E XE X X X D T Q

X X

• 42 test geometries (including global minimum region)

• Only

extrapolated

• Extrapolation with double- and triple- zeta basis sets sufficient here

formula of Halkier et al. [CPL 286 (1998) 243]

Intermolecular potential energy surface of the Acetylene-Benzene dimer: Choice of geometries

Grid Definition

3.0 ≤ R ≤ 7.0 Å R ↑ by 0.5 Å

0 ≤ Θ ≤ 90°

0 ≤ Φ ≤ 30°

0 ≤ θ ≤ 90°

0 ≤ φ ≤ 180°

All angles ↑ by 30 °

Resulting Grid

8 × 4 × 2 × 4 × 7 = 1792

1792 – 1099 = 693

C. A. Hunter et al. J. Am. Chem. Soc. 112 (1990), 5525

J. Gauss et al. J. Phys. Chem. 104 (2000),2865

J. L. M. Martin et al. J. Chem. Phys. 108 (1998), 676


Asymptotic interactions: Electrostatic energy via multipole expansion and Dispersion energy

Quadrupole-Quadrupoleinteraction

Quadrupole-Octapoleinteraction

Octapole-Octapoleinteraction

•Quadrupole moments and Dispersion coefficients are calculated only once.•Rotated for other orientations using Euler`s rotation matrices.•10.0 ≤ R ≤ 49.0 Å, R increased by 3 Å •10192 orientations produced in this manner.•10192 + 693 = 10885 (Total number of points used in fit procedure)

Fitting the intermolecular PES: Fit of extrapolated total interaction energy

Repulsion Dispersion&

Induction

Electrostatics

• Site-site fit model:

• Merit function (Chi-Square):

• Damping function:

C. Leforestier, A. Tekin, G. Jansen , M. Herman, J. Chem. Phys., 135, 234306, (2011)


Fitting the intermolecular PES: Fit quality I

-唴唴

For 693 points SD [kJ/mol]: 3.63

2.6 Eint [kJ/mol]

0.18 6.9 (15.5 %)-唴唴

For 10885 points SD [kJ/mol]: 0.92

2.6 Eint [kJ/mol]

0.04 6.9 (15.5 %)


Fitting the intermolecular PES: Fit quality II


Fitting the intermolecular PES: Fit quality III

R (Å) 4.3 5.7 8.5

Θ1 15° 80°

Φ1 15°

Θ2 20° 50°

Φ2 25° 145°


Attention!!

Turbomole15.06.2012

Fitting the intermolecular PES: Comparison to Experiment

(SS1)

They “confirmed” the existence of 1B employingHF, MP2 and B3LYP with 6-31G++(d,p) geometry optimizations.


Intermolecular potential energy surface of the Acetylene - Acetylene dimer: Choice of geometriesGrid Definition

3.0 ≤ R ≤ 7.0 Å R ↑ by 0.5 Å

0 ≤ Θ1 ≤ 90°

0 ≤ Θ2 ≤ 180°

0 ≤ Φ2 ≤ 360°

Θ1 ↑ by 15 °

Θ2 and Φ2 ↑ by 30 °

Resulting Grid

9 × 7 × 7 × 13 = 5733

5733 – 4904 = 829

C. Leforestier, A. Tekin, G. Jansen , M. Herman, J. Chem. Phys., 135, 234306, (2011)


Intermolecular potential energy surface of the Benzene - Benzene dimer: Choice of geometries Grid Definition

3.0 ≤ R ≤ 7.0 Å R ↑ by 1 Å

0 ≤ Θ ≤ 90°

0 ≤ Φ ≤ 30°

0 ≤ φ ≤ 360°

0 ≤ θ ≤ 360°

0 ≤ ω ≤ 360°

All angles ↑ by 30 °

Resulting Grid

5 × 4 × 2 × 13 × 13 × 13 = 87880

87880 – 86532 = 1348


AcnBz cluster geometry optimizations: Test system Ac2Bz

RingD

6h C2V

(kcal/mol) Ring D6h C2V

MP2/VDZa 0.106 0. 1.517

MP2/TZVP 0. 0.580

2.165

MP2/VDZ/CP 0. 0.241

1.297

Model 0. 0.241

1.401a Fujii et al. J. Phys. Chem. A 108 (2004) 2652.


Structural comparison of Ac2Bz geometries

A

B

C

D

E

F

G

H

(Å) AB AC DE DF DG DH

MP2/TZVP 2.81 2.61 2.66 2.66 2.69 2.68

MP2/VDZ/CP 2.90 2.82 2.82 2.82 2.91 2.91

Model 2.85 2.72 2.82 2.82 2.85 2.85

A

B

C

(Å) AB AC

MP2/TZVP 4.69 2.73

MP2/VDZ/CP 5.15 2.93

Model 4.96 2.85


Acn (n=3-6) clusters

-7.11

-10.79

-10.73

-14.82

-14.46

-19.30

(Energies are in mH)


AcnBz (n=3-6) clusters

-13.51-13.49

-19.11

-24.43-30.52 -29.99



Ac1Bz2 clusters

-8.74-10.53

-8.31

A

Angew. Chem. Int. Ed. 47 (2008) 10094



Ac2Bz2 clusters

-16.25

-13.36

-15.23

-15.39

-14.97

-12.97

-15.49

-15.04-15.37



Intermolecular interactions [in kJ/mol] in water dimerBasis HF MP2 SCS-MP2 B3LYP-D PBE0 LPBE0 CCSD(T)

AVDZ -15.891390 -18.803673 -17.166490 -21.639948 -17.386616 -18.428262 -18.660504

AVTZ -15.765523 -19.932165 -18.160662 -21.843949 -18.707867 -19.887984 -20.067011

AVQZ -15.908823 -20.559949 -18.804303 -22.006363 -19.133093 -20.337871 -20.733232

— Molpro energy results are in hartree. Convert them to kJ/mol by multiplying 2625.5.— DFT-SAPT results are in mH (mili Hartree). Multiply them by 2.6255.— HF, MP2, SCS-MP2, CCSD and CCSD(T) results are in CCSD(T) outputs.— Only the SCS-MP2 interaction energy is not written in the output. To calculate it grep SCS-MP2 energies in the ccsd(t) outputs:— grep "SCS-MP2 total energy" water-ccsdt-avdz.out

ESCS-MP2=(-152.52056354-(-76.25674577-76.25727940)) in hartree


Typical CCSD(T) output

!RHF STATE 1.1 EnergyMP2 total energySCS-MP2 total energy !CCSD(T) total energy

SETTING E_MB_CP_MP2 = -76.26175127 AU SETTING E_MB_CP_CCSD = -76.26944486 AU SETTING E_MB_CP_CCSDT = -76.27482665 AU SETTING E_INT_HF = -0.00605271 AU SETTING E_INT_MP2 = -0.00716194 AU SETTING E_INT_CCSD = -0.00685369 AU SETTING E_INT_CCSDT = -0.00710741 AU


Typical CCSD(T) output

cp water-ccsdt-avdz.com water-ccsdt-avtz.comcp water-ccsdt-avtz.com water-ccsdt-avqz.com


Typical DFT-SAPT output

SETTING DHF = -1.15745486 mH

=========== IMW Results =========== [mH] [kcal/mol] [kJ/mol] E1pol -11.45483815 ( -0.11454838E+02) -7.1880 -30.0747 E1exch 10.21741485 ( 0.10217415E+02) 6.4115 26.8258 E1exch(S2) 10.15101824 ( 0.10151018E+02) 6.3699 26.6515 E2ind -3.98070553 ( -0.39807055E+01) -2.4979 -10.4513 E2ind-exch 2.32414481 ( 0.23241448E+01) 1.4584 6.1020 E2disp(unc) -4.50262689 ( -0.45026269E+01) -2.8254 -11.8216 E2disp -3.17861613 ( -0.31786161E+01) -1.9946 -8.3455 E2disp-exch(unc) 0.79013747 ( 0.79013747E+00) 0.4958 2.0745 E2disp-exch 0.60784335 ( 0.60784335E+00) 0.3814 1.5959

E1tot -1.23742331 ( -0.12374233E+01) -0.7765 -3.2489 E2tot -4.22733350 ( -0.42273335E+01) -2.6527 -11.0989 E1tot+E2tot -5.46475681 ( -0.54647568E+01) -3.4292 -14.3477

SETTING ETOTAL = -6.62221167 mH


I. Supermolecular CCSD(T) input (http://www.be.itu.edu.tr/~adem.tekin/molpro/water-ccsdt-avdz.com)

memory,550,mgthresh,energy=1d-8,orbital=1d-7

basis,default=avdz

!nosym, ! IF THERE IS NO SYMMETRYsymmetry,zangstromGEOMTERY={O1,, 0.1134349, -1.6972642, 0.0000000H1,, -0.0489012, -0.7388274, 0.0000000H2,, -0.7694849, -2.0866817, 0.0000000O2,, -0.0837066, 1.2726931, 0.0000000H3,, 0.3943289, 1.6250401, 0.7627674H4,, 0.3943289, 1.6250401, -0.7627674}int

Turbomole

II. Supermolecular CCSD(T) input

! --- dimer ---hfe_dim_hf=energyccsd(t)e_dim_mp2=emp2e_dim_ccsd=energce_dim_ccsdt=energt(1)

! --- monomerA-CP ---dummy,O2,H3,H4hfe_mA_CP_hf=energyccsd(t)e_mA_CP_mp2=emp2e_mA_CP_ccsd=energce_mA_CP_ccsdt=energt(1)


III. Supermolecular CCSD(T) input

! --- monomerB-CP ---dummy,O1,H1,H2hfe_mB_CP_hf=energyccsd(t)e_mB_CP_mp2=emp2e_mB_CP_ccsd=energce_mB_CP_ccsdt=energt(1)

e_int_hf = e_dim_hf - e_mA_CP_hf - e_mB_CP_hfe_int_mp2 = e_dim_mp2 - e_mA_CP_mp2 - e_mB_CP_mp2e_int_ccsd=e_dim_ccsd-e_mA_CP_ccsd-e_mB_CP_ccsde_int_ccsdt=e_dim_ccsdt-e_mA_CP_ccsdt-e_mB_CP_ccsdt

I. Density Fitting MP2 input (http://www.be.itu.edu.tr/~adem.tekin/molpro/water-mp2-avdz.com)

memory,200,mgdirectgthresh,energy=1d-8,orbital=1d-7basis={default,avdzset,mp2fitdefault,avdz/MP2FITset,jkfitdefault,vtz/jkfit}nosym,angstromGEOMTERY={O1,, 0.1134349, -1.6972642, 0.0000000H1,, -0.0489012, -0.7388274, 0.0000000H2,, -0.7694849, -2.0866817, 0.0000000O2,, -0.0837066, 1.2726931, 0.0000000H3,, 0.3943289, 1.6250401, 0.7627674H4,, 0.3943289, 1.6250401, -0.7627674}int

II. Density Fitting MP2 input! --- dimer ---df-hf,basis=jkfit,locfit=0e_dim_hf=energydf-mp2,basis=mp2fit,locfit=0e_dim_mp2=emp2

! --- monomerA-CP ---dummy,O2,H3,H4df-hf,basis=jkfit,locfit=0e_mA_CP_hf=energydf-mp2,basis=mp2fit,locfit=0e_mA_CP_mp2=emp2

! --- monomerB-CP ---dummy,O1,H1,H2df-hf,basis=jkfit,locfit=0e_mB_CP_hf=energydf-mp2,basis=mp2fit,locfit=0e_mB_CP_mp2=emp2

e_int_hf = e_dim_hf - e_mA_CP_hf - e_mB_CP_hfe_int_mp2 = e_dim_mp2 - e_mA_CP_mp2 - e_mB_CP_mp2


Basis set selection for water-b3lyp-d-avdz.com

for AVDZ

basis={default,avdzset,jkfitdefault,vtz/jkfitset,mp2fitdefault,avdz/mp2fit}

for AVTZ

basis={default,avtzset,jkfitdefault,vqz/jkfitset,mp2fitdefault,avtz/mp2fit}

for AVQZ

basis={default,avqzset,jkfitdefault,v5z/jkfitset,mp2fitdefault,avqz/mp2fit}

I. DFT-SAPT (PBE0AC) input (http://www.be.itu.edu.tr/~adem.tekin/molpro/water-pbe0-avdz.com)

memory,170,mgdirectgthresh,energy=1d-8,orbital=1d-8symmetry,nosymorient,noorientGEOMTERY={angstrom;! water1,O1,, 0.1134349, -1.6972642, 0.00000002,H1,, -0.0489012, -0.7388274, 0.00000003,H2,, -0.7694849, -2.0866817, 0.00000004,O2,, -0.0837066, 1.2726931, 0.00000005,H3,, 0.3943289, 1.6250401, 0.76276746,H4,, 0.3943289, 1.6250401, -0.7627674}basis={default,avdzset,jkfitdefault,vtz/jkfitset,mp2fitdefault,avdz/mp2fit}int


II. DFT-SAPT (PBE0AC) input

ca=2101.2cb=2102.2

!--HF-------------df-hf,basis=jkfit,locfit=0edm=energy

dummy,O2,H3,H4df-hf,basis=jkfit,locfit=0save,$caema=energysapt;monomerA

dummy,O1,H1,H2{df-hf,basis=jkfit,locfit=0; start,atdenssave,$cb}emb=energysapt;monomerB


III. DFT-SAPT (PBE0AC) input

{grid;gridthr,1d-6}{sapt,SAPT_NFRQ_DISP=8;intermol,saptlevel=2,ca=$ca,cb=$cb,icpks=1,fitlevel=3dfit,basis_coul=jkfit,basis_exch=jkfit,basis_mp2=mp2fit,cfit_scf=3}dHF=(edm-ema-emb)*1000.-e1pol-e1ex-e2ind-e2exind

!--DFT------------grid;gridthr,1d-8

ca=2103.2cb=2104.2

dummy,O2,H3,H4df-ks,pbe0asymp,0.13,0.5,40,0.05 ! 0.13= Ionization energy - HOMOdfit,basis=jkfit,locfit=0save,$casapt;monomerA


IV. DFT-SAPT (PBE0AC) input

dummy,O1,H1,H2dfit,basis=jkfit,locfit=0{df-ks,pbe0; asymp,0.13,0.5,40,0.05; start,atdenssave,$cb}sapt;monomerB

grid;gridthr,1d-6{sapt,SAPT_LEVEL=3,SAPT_NFRQ_DISP=8;intermol,ca=$ca,cb=$cb,icpks=1,fitlevel=3,nlexfac=0.0dfit,basis_coul=jkfit,basis_exch=jkfit,basis_mp2=mp2fit,cfit_scf=3}

Etotal=e1pol+e1ex+e2ind+e2exind+e2disp+e2exdisp+dHF

I. DFT-SAPT (LPBE0AC) input (http://www.be.itu.edu.tr/~adem.tekin/molpro/water-lpbe0-avdz.com)

memory,300,mgdirectgthresh,energy=1d-8,orbital=1d-8symmetry,nosymorient,noorientGEOMTERY={angstrom;! water1,O1,, 0.1134349, -1.6972642, 0.00000002,H1,, -0.0489012, -0.7388274, 0.00000003,H2,, -0.7694849, -2.0866817, 0.00000004,O2,, -0.0837066, 1.2726931, 0.00000005,H3,, 0.3943289, 1.6250401, 0.76276746,H4,, 0.3943289, 1.6250401, -0.7627674}

basis={set,orbital; default,avdzset,jkfit; default,avdz/jkfitset,mp2fit; default,avdz/mp2fitset,dflhf; default,avdz/jkfit}


II. DFT-SAPT (LPBE0AC) input

ca=2101.2cb=2102.2

!--HF-------------df-hf,basis=jkfit,locorb=0edm=energy

dummy,O2,H3,H4df-hf,basis=jkfit,locorb=0save,$caema=energysapt;monomerA

dummy,O1,H1,H2{df-hf,basis=jkfit,locorb=0save,$cb}emb=energysapt;monomerB

III. DFT-SAPT (LPBE0AC) input{grid;gridthr,1d-6}{sapt,SAPT_NFRQ_DISP=8;intermol,saptlevel=2,ca=$ca,cb=$cb,icpks=1,fitlevel=3dfit,basis_coul=jkfit,basis_exch=jkfit,,basis_mp2=mp2fit,cfit_scf=3}dHF=(edm-ema-emb)*1000.-e1pol-e1ex-e2ind-e2exind

!--DFT------------grid;gridthr,1d-8

ca=2103.2cb=2104.2

shift_pyr1=0.13shift_pyr2=0.13

!monomer A, perform LPBE0AC calculationdummy,O2,H3,H4{df-ks,pbex,pw91c,lhf; dftfac,0.75,1.0,0.25; asymp,shift_pyr1; save,$ca}sapt;monomerA


IV. DFT-SAPT (LPBE0AC) input

!monomer B, perform LPBE0AC calculationdummy,O1,H1,H2{df-ks,pbex,pw91c,lhf; dftfac,0.75,1.0,0.25; start,atdens; asymp,shift_pyr2; save,$cb}sapt;monomerB

grid;gridthr,1d-6{sapt,SAPT_LEVEL=3,SAPT_NFRQ_DISP=8;intermol,ca=$ca,cb=$cb,icpks=1,fitlevel=3,nlexfac=0.0dfit,basis_coul=jkfit,basis_exch=jkfit,basis_mp2=mp2fit,cfit_scf=3}

Etotal=e1pol+e1ex+e2ind+e2exind+e2disp+e2exdisp+dHF


DFT-SAPT energy components

Component AVDZ AVTZ AVQZ DHF -3.0389 -3.0862 -3.1033 E1pol -30.0747 -30.0541 -30.1058 E1exch 26.8258 26.8072 26.7828 E1exch(S2) 26.6515 26.6339 26.6098 E2ind -10.4513 -10.9696 -10.9495 E2ind-exch 6.1020 6.5146 6.4726 E2disp(unc) -11.8216 -13.3978 -13.8237 E2disp -8.3455 -9.8115 -10.2466 E2disp-exch(unc) 2.0745 2.3636 2.4813 E2disp-exch 1.5959 1.8918 2.0167

E1tot -3.2489 -3.2469 -3.3230 E2tot -11.0989 -12.3748 -12.7068 E1tot+E2tot -14.3477 -15.6217 -16.0298

Eint -17.3866 -18.7079 -19.1330

molpro a quantum chemistry package adem tekin yrd. doc. dr. 15.06.2012 istanbul

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