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33 SYMMETRY-ADAPTED INTERMOLECULAR PERTURBATION THEORY 247 r=dist(i) !monomer A dummy,he2 {hf; save,$ca} sapt;monomerA !monomer B dummy,he1 {hf; start,atdens; save,$cb} sapt;monomerB !interaction contributions sapt;intermol,ca=$ca,cb=$cb elst(i)=E1pol; exch(i)=E1ex ind(i)=E2ind; exind(i)=E2exind disp(i)=E2disp; exdisp(i)=E2exdisp etot(i)=E12tot data,truncate,$ca enddo {table,dist,elst,exch,ind,exind,disp,exdisp,etot ftyp,d,d,d,d,d,d,d,d,d plot} yields the plot 0.4 ELST EXCH IND EXIND DISP EXDISP ETOT 0.2 0 -0.2 4.5 5 5.5 6 6.5 7 DIST Currently SAPT only accepts single-determinant wave functions for the monomers, i.e. from Hartree-Fock or Kohn-Sham DFT (see next section) calculations. This means that if Hartree- Fock wave functions are used for monomer, the following quantity is obtained (zero in superscript denotes that no intramonomer correlation is accounted for) [1]. E SAPT = E (10) pol + E (10) exch + E(20) ind,resp. + E(20) exch−ind,resp. + E(20) disp + E(20) exch−disp No point group symmetry can be exploited in a SAPT calculation.
33 SYMMETRY-ADAPTED INTERMOLECULAR PERTURBATION THEORY 248 33.3 DFT-SAPT It is of crucial importance to account for the intramolecular correlation effects of the individual SAPT terms since Hartree-Fock theory often yields poor first- and second-order electrostatic properties. While this can be done using many-body perturbation theory [1] (in a double perturbation theory ansatz) a more efficient way is to use static and time-dependent DFT theory. This variant of SAPT, termed as DFT-SAPT [2-6], has in contrast to Hartree-Fock-SAPT the appealing feature that the polarisation terms (E (1) pol , E(2) ind , E(2) disp ) are potentially exact, i.e. they come out exactly if the exact exchange-correlation (xc) potential and the exact (frequency-dependent) xc response kernel of the monomers were known. On the other hand, this does not hold for the exchange terms since Kohn-Sham theory can at best give a good approximation to the exact density matrix of a many-body system. It has been shown [6] that this is indeed the the case and therefore DFT-SAPT has the potential to produce highly accurate interaction energies comparable to high-level supermolecular many-body perturbation or coupled cluster theory. However, in order to achieve this accuracy, it is of crucial importance to correct the wrong asymptotic behaviour of the xc potential in current DFT functionals [3-5]. This can be done by using e.g.: {ks,lda; asymp,} which activates the gradient-regulated asymptotic correction approach of Grüning et al. (J. Chem. Phys. 114, 652 (2001)) for the respective monomer calculation. The user has to supply a shift parameter (∆ xc ) for the bulk potential which should approximate the difference between the HOMO energy (ε HOMO ) obtained from the respective standard Kohn-Sham calculation and the (negative) ionisation potential of the monomer (IP): ∆ xc = ε HOMO − (−IP) (63) This method accounts for the derivative discontinuity of the exact xc-potential and that is missing in approximate ones. Note that this needs to be done only once for each system. (See also section 33.7.2 for an explicit example). Concerning the more technical parameters in the DFT monomer calculations it is recommended to use lower convergence thresholds and larger intergration grids compared to standard Kohn- Sham calculations. 33.4 High order terms It has been found that third and higher-order terms become quite important if one or both monomers are polar. As no higher than second-order terms are currently implemented in SAPT, one may use a non-correlated estimation of those terms by using supermolecular Hartree-Fock (see e.g. [7]). This can be done by adapting the following template: !dimer hf edm=energy !monomer A dummy, {hf; save,$ca} ema=energy
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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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18 ORBITAL LOCALIZATION 126 GROUP,3
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18 ORBITAL LOCALIZATION 128 18.9 Op
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19 THE MCSCF PROGRAM MULTI 130 f) c
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19 THE MCSCF PROGRAM MULTI 132 19.3
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19 THE MCSCF PROGRAM MULTI 134 WF,6
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19 THE MCSCF PROGRAM MULTI 138 or C
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19 THE MCSCF PROGRAM MULTI 144 icst
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20 THE CI PROGRAM 148 ***,N2 geomet
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20 THE CI PROGRAM 150 and double ex
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20 THE CI PROGRAM 152 refstat: mxsh
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20 THE CI PROGRAM 154 Default is to
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20 THE CI PROGRAM 156 20.3.8 Restri
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20 THE CI PROGRAM 158 DM and NATORB
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20 THE CI PROGRAM 160 ZERO: THRDLP:
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20 THE CI PROGRAM 162 PAIRS=1: prin
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20 THE CI PROGRAM 164 problem is to
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21 MULTIREFERENCE RAYLEIGH SCHRÖDI
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22 NEVPT2 CALCULATIONS 176 IHINT=0
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23 MØLLER PLESSET PERTURBATION THE
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23 MØLLER PLESSET PERTURBATION THE
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24 THE CLOSED SHELL CCSD PROGRAM 18
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25 EXCITED STATES WITH EQUATION-OF-
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Page 229 and 230: 27 THE MRCC PROGRAM OF M. KALLAY (M
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Page 237 and 238: 29 LOCAL CORRELATION TREATMENTS 204
Page 257 and 258: 30 LOCAL METHODS FOR EXCITED STATES
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Page 261 and 262: 31 EXPLICITLY CORRELATED METHODS 22
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Page 289 and 290: 34 PROPERTIES AND EXPECTATION VALUE
Page 301 and 302: 35 RELATIVISTIC CORRECTIONS 268 •
Page 303 and 304: 36 DIABATIC ORBITALS 270 This proce
Page 305 and 306: 37 NON ADIABATIC COUPLING MATRIX EL
Page 307 and 308: 38 QUASI-DIABATIZATION 274 This cal
Page 309 and 310: 38 QUASI-DIABATIZATION 276 ***,h2s
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Page 313 and 314: 39 THE VB PROGRAM CASVB 280 39 THE
Page 315 and 316: 39 THE VB PROGRAM CASVB 282 configu
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Page 325 and 326: 40 SPIN-ORBIT-COUPLING 292 integral
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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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