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22 NEVPT2 CALCULATIONS 177 • Strict separability (size consistence): the energy of a collection of non–interacting systems equals the sum of the energies of the isolated systems • Absence of intruder states: the zero-order energies associated to the functions of the outer space are well separated from the zero-order energy of the state being studied, thus avoiding divergences in the perturbation summation • The first order correction to the wavefunction is an eigenfunction of the spin operators S 2 and S z • Electronically excited states are dealt with at the same level of accuracy as the ground state • NEVPT2 energies are invariant under a unitary transformation of the active orbitals. Furthermore, the choice of canonical orbitals for the core and virtual orbitals (the default choice) ensure that the results coincide with those of an enlarged version of the theory fully invariant under rotations in the core and virtual orbital spaces, respectively • NEVPT2 coincides with MP2 in the case of a HF wave function NEVPT2 has been implemented in two variants both of which are present in <strong>MOLPRO</strong>, these are the strongly contracted (SC) and the partially contracted (PC) variants. The two variants differ by the number of perturber functions employed in the perturbation summation. The PC– NEVPT2 uses a richer function space and is in general more accurate than the SC–NEVPT2. The results of SC–NEVPT2 and PC–NEVPT2 are anyway usually very close to one another. 22.2 Input description NEVPT2 must follow a CAS–SCF or CAS–CI calculation. The command NEVPT2,options has to be specified to carry out a second–order perturbation calculation. NEVPT2 is part of the MRCI program and uses the options of the latter. Of particular relevance are the options CORE, CLOSED, OCC, WF and STATE of the MRCI program. There is, at the moment, only one option specific to NEVPT2 which can be provided by the user: THRNEVPT2 The threshold to discard small coefficients in the CAS wavefunction (default = 0.0), The present implementation of NEVPT2 is state–specific, i.e. the perturbation theory can only be applied to a single state. The multi–state (or quasi–degenerate) version of NEVPT2 will be implemented in <strong>MOLPRO</strong> in the near future. An example is provided where the energies of the ground state and of the first 1 A 2 (n → π ∗ ) excited state of formaldehyde are calculated.
23 MØLLER PLESSET PERTURBATION THEORY 178 ***, memory,20,m file,1,h2co.int file,2,h2co.wf gthresh,energy=1.d-9 gthresh,orbital=1.d-8 gthresh,civec=1.d-8 geomtyp=zmat geometry O,, 0.000000000, 0.000000000, 0.0196594609 C,, 0.000000000, 0.000000000, 2.3248507925 H1,, 0.000000000, 1.7597110083, 3.3972521023 H2,, 0.000000000, -1.7597110083, 3.3972521023 end basis=6-31G* {hf wf,16,1,0} {multi closed,4,0,1,0 occ,6,2,4,0 wf,16,1,0 state,1 natorb,2140.2,state=1.1 } {nevpt2,thrden=1.0d-10,thrvar=1.0d-10 core,2,0,0,0 closed,4,0,1,0 occ,6,2,4,0 orbit,2140.2,state=1.1 wf,16,1,0 state,1,1 } {multi closed,4,0,1,0 occ,6,2,4,0 wf,16,4,0 state,1 start,2140.2 natorb,2141.2,state=1.4 } {nevpt2,thrden=1.0d-10,thrvar=1.0d-10 core,2,0,0,0 closed,4,0,1,0 occ,6,2,4,0 orbit,2141.2,state=1.4 wf,16,4,0 state,1,1 } http://www.molpro.net/info/current/examples/form_nevpt2.com 23 MØLLER PLESSET PERTURBATION THEORY Closed-shell Møller-Plesset perturbation theory up to full fourth order [MP4(SDTQ)] is part of the coupled-cluster program.
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MOLPRO Users Manual Version 2010.1
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ii • Møller-Plesset perturbation
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iv 3. Explicitly correlated LMP2-F1
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vi The original reference to uncont
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viii Rangehybrid methods: T. Leinin
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CONTENTS x 4.12 Summary of keywords
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CONTENTS xii 10.4 Geometry Files .
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CONTENTS xiv 16.9.4 Sanity check on
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CONTENTS xvi 19.5.1 Defining the st
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CONTENTS xviii 20.4 Miscellaneous t
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CONTENTS xx 29.6.3 Manually Definin
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CONTENTS xxii 34.1.5 Printing optio
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CONTENTS xxiv 39.10Point group symm
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CONTENTS xxvi 42.2.7 Numerical Hess
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CONTENTS xxviii 53 QM/MM INTERFACES
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CONTENTS xxx A.3.11 Fedora 13 (32-b
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CONTENTS xxxii C.41 THGFL: . . . .
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2 RUNNING MOLPRO 2 of directories o
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2 RUNNING MOLPRO 4 also some parts
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2 RUNNING MOLPRO 6 Note that option
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3 DEFINITION OF MOLPRO INPUT LANGUA
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4 GENERAL PROGRAM STRUCTURE 14 Glob
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4 GENERAL PROGRAM STRUCTURE 16 in d
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4 GENERAL PROGRAM STRUCTURE 18 Tabl
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4 GENERAL PROGRAM STRUCTURE 20 tion
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4 GENERAL PROGRAM STRUCTURE 22 Prog
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4 GENERAL PROGRAM STRUCTURE 24 LCIS
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5 INTRODUCTORY EXAMPLES 26 In the a
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5 INTRODUCTORY EXAMPLES 28 5.7 Proc
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6 PROGRAM CONTROL 30 ***,h2o benchm
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6 PROGRAM CONTROL 32 6.5 Allocating
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6 PROGRAM CONTROL 34 6.7.1 IF state
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6 PROGRAM CONTROL 36 Certain import
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6 PROGRAM CONTROL 38 ZERO ONEINT TW
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6 PROGRAM CONTROL 40 6.13.1 Example
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6 PROGRAM CONTROL 42 Table 5: One-e
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7 FILE HANDLING 44 7.4 DATA The DAT
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8 VARIABLES 46 Numbers: Logicals: S
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8 VARIABLES 48 8.4 System variables
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8 VARIABLES 50 are valid variable d
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8 VARIABLES 52 CM=1.d0/219474.63067
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8 VARIABLES 54 DEL4 ∇ 4 DARWIN Da
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8 VARIABLES 56 CHARGE NELEC SPIN CI
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9 TABLES AND PLOTTING 58 8.11 Readi
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9 TABLES AND PLOTTING 60 plotted; i
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10 MOLECULAR GEOMETRY 62 PLANEXZ z-
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10 MOLECULAR GEOMETRY 64 geometry s
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10 MOLECULAR GEOMETRY 66 ***,H2O ge
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10 MOLECULAR GEOMETRY 68 entries. D
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11 BASIS INPUT 70 resolution in exp
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11 BASIS INPUT 72 • The Binning/C
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11 BASIS INPUT 74 The specification
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11 BASIS INPUT 76 the exponents of
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11 BASIS INPUT 78 ***,h2o geom={o;
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12 EFFECTIVE CORE POTENTIALS 80 is
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13 CORE POLARIZATION POTENTIALS 82
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14 INTEGRATION 84 14.1 Sorted integ
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14 INTEGRATION 86 smaller than this
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14 INTEGRATION 88 THR D3EXT THREST
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14 INTEGRATION 90 THRQ2 LMP2 THRAO
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14 INTEGRATION 92 Table 7: Default
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15 DENSITY FITTING 94 DF-HF,DF_BASI
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15 DENSITY FITTING 96 LOCFIT F12 LO
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16 THE SCF PROGRAM 98 16 THE SCF PR
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16 THE SCF PROGRAM 100 16.1.4 Optio
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16 THE SCF PROGRAM 102 16.3 Saving
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16 THE SCF PROGRAM 104 r1=1.85,r2=1
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16 THE SCF PROGRAM 106 16.9.1 Level
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17 THE DENSITY FUNCTIONAL PROGRAM 1
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18 ORBITAL LOCALIZATION 124 geometr
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Page 199 and 200: 21 MULTIREFERENCE RAYLEIGH SCHRÖDI
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Page 229 and 230: 27 THE MRCC PROGRAM OF M. KALLAY (M
Page 235 and 236: 28 SMILES 202 This code is not incl
Page 237 and 238: 29 LOCAL CORRELATION TREATMENTS 204
Page 257 and 258: 30 LOCAL METHODS FOR EXCITED STATES
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31 EXPLICITLY CORRELATED METHODS 22
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32 THE FULL CI PROGRAM 244 32 THE F
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33 SYMMETRY-ADAPTED INTERMOLECULAR
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34 PROPERTIES AND EXPECTATION VALUE
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35 RELATIVISTIC CORRECTIONS 268 •
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36 DIABATIC ORBITALS 270 This proce
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37 NON ADIABATIC COUPLING MATRIX EL
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38 QUASI-DIABATIZATION 274 This cal
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38 QUASI-DIABATIZATION 276 ***,h2s
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38 QUASI-DIABATIZATION 278 ***,h2s
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39 THE VB PROGRAM CASVB 280 39 THE
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39 THE VB PROGRAM CASVB 282 configu
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39 THE VB PROGRAM CASVB 284 be proj
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39 THE VB PROGRAM CASVB 286 The lis
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39 THE VB PROGRAM CASVB 288 This ke
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39 THE VB PROGRAM CASVB 290 to writ
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40 SPIN-ORBIT-COUPLING 292 integral
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40 SPIN-ORBIT-COUPLING 294 40.6.1 P
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40 SPIN-ORBIT-COUPLING 296
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41 ENERGY GRADIENTS 298 41 ENERGY G
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41 ENERGY GRADIENTS 300 state2) and
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41 ENERGY GRADIENTS 302 ZMAT OPT3N
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42 GEOMETRY OPTIMIZATION (OPTG) 304
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43 VIBRATIONAL FREQUENCIES (FREQUEN
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45 MINIMIZATION OF FUNCTIONS 340 45
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45 MINIMIZATION OF FUNCTIONS 342 **
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46 BASIS SET EXTRAPOLATION 344 extr
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46 BASIS SET EXTRAPOLATION 346 ***,
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46 BASIS SET EXTRAPOLATION 348 46.3
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46 BASIS SET EXTRAPOLATION 350 geom
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47 POTENTIAL ENERGY SURFACES (SURF)
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48 POLYNOMIAL REPRESENTATIONS (POLY
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49 THE VSCF PROGRAM (VSCF) 364 THER
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50 THE VCI PROGRAM (VCI) 366 CITHR=
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50 THE VCI PROGRAM (VCI) 368 surf,s
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52 THE COSMO MODEL 370 52 THE COSMO
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52 THE COSMO MODEL 372 or using the
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54 THE TDHF AND TDKS PROGRAMS 374 o
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55 ORBITAL MERGING 376 MOVE command
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55 ORBITAL MERGING 378 55.13 Exampl
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56 MATRIX OPERATIONS 380 ***,NO mer
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56 MATRIX OPERATIONS 382 56.2 Loadi
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56 MATRIX OPERATIONS 384 If NATURAL
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56 MATRIX OPERATIONS 386 56.14 Form
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56 MATRIX OPERATIONS 388 ***,h2o ma
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A INSTALLATION GUIDE 390 the result
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A INSTALLATION GUIDE 392 For IA32 L
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A INSTALLATION GUIDE 394 3. If any
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A INSTALLATION GUIDE 396 -gfortran
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A INSTALLATION GUIDE 398 A.3.7 Test
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A INSTALLATION GUIDE 400 --noverbos
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A INSTALLATION GUIDE 402 A.3.12 ope
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A INSTALLATION GUIDE 404 A.3.14 Ins
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B RECENT CHANGES 406 B.1.4 New basi
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B RECENT CHANGES 408 1) · exp(−9
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B RECENT CHANGES 410 B.4 New featur
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B RECENT CHANGES 412 5. Multipole m
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C DENSITY FUNCTIONAL DESCRIPTIONS 4
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+ 9 8 (1 − ζ ) 4/3 C DENSITY FUN
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D LICENSE INFORMATION 456 D.1 BLAS
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D LICENSE INFORMATION 458 D.3 Boost
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INDEX 460 DFTTHRESH, 109 Difference
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INDEX 462 NOGPRINT, 38 NOGRIDSAVE,
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