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38 QUASI-DIABATIZATION 277 This calculation produces the following results: Diabatic energies for H2S, obtained from CI-vectors R E1 E2 H11CI H22CI H21CI 2.50 -398.64296319 -398.63384782 -398.64296319 -398.63384782 0.000000 2.55 -398.64572746 -398.63666636 -398.64509901 -398.63729481 -0.002302 2.60 -398.64911752 -398.63771802 -398.64662578 -398.64020976 -0.004711 Diabatic energies for H2S, obtained from CI-vectors and orbital correction R E1 E2 H11 H22 H21 2.50 -398.64296319 -398.63384782 -398.64296319 -398.63384782 0.000000 2.55 -398.64572746 -398.63666636 -398.64509941 -398.63729441 -0.002301 2.60 -398.64911752 -398.63771802 -398.64662526 -398.64021027 -0.004711 The results in the first table are obtained from the CI-contribution to the state-overlap matrix only, while the ones in the second table include a first-order correction for the orbitals. In this case, both results are almost identical, since the DIAB procedure has been used to minimize the change of the active orbitals. This is the recommended procedure. If simply natural orbitals are used without orbital diabatization, the following results are obtained from the otherwise unchanged calculation: Diabatic energies for H2S, obtained from CI-vectors R E1 E2 H11CI H22CI H21CI 2.50 -398.64296319 -398.63384782 -398.64296319 -398.63384782 0.000000 2.55 -398.64572742 -398.63666630 -398.64475612 -398.63763760 -0.002803 2.60 -398.64911746 -398.63771803 -398.64521031 -398.64162518 -0.005410 Diabatic energies for H2S, obtained from CI-vectors and orbital correction R E1 E2 H11 H22 H21 2.50 -398.64296319 -398.63384782 -398.64296319 -398.63384782 0.000000 2.55 -398.64572742 -398.63666630 -398.64509146 -398.63730226 -0.002314 2.60 -398.64911746 -398.63771803 -398.64648358 -398.64035190 -0.004804 It is seen that the mixing obtained from the CI vectors only is now very different and meaningless, since the orbitals change significantly as function of geometry. However, the second calculations, which accounts for this change approximately, still gives results in quite good agreement with the calculation involving diabatic orbitals. The final examples shows a more complicated input, which also computes the non-adiabatic coupling matrix elements. In a two-state model, the NACME should equal the first derivative of the mixing angle. In the example, the NACME is computed using the 3-point DDR method (NACMECI), and also by finite difference of the mixing angle (DCHI).
38 QUASI-DIABATIZATION 278 ***,h2s Diabatization and NACME calculation memory,3,m gprint,orbitals,civector symmetry,x orient,noorient geometry={ s; h1,s,r1; h2,s,r2,h1,theta} basis=avdz r1=2.5 theta=[92] r=[2.55,2.60] dr=[0,0.01,-0.01] reforb1=2140.2 refci=6000.2 savci=6100.2 !noorient should always be used for diabatization !This basis is too small for real application !Reference geometry !Displaced geometries !Samll displacements for finite difference NACME calculation !Orbital dumprecord at reference geometry !MRCI record at reference geometry !MRCI record at displaced geometries text,compute wavefunction at reference geometry (C2v) r2=r1 {hf;occ,9,2;wf,18,2,4;orbital,2100.2} {multi;occ,9,2;closed,4,1; wf,18,2;state,2; natorb,reforb1 noextra} {ci;occ,9,2;closed,4,1; wf,18,2,0;state,2; orbital,reforb1 save,refci} !1B1 and 1A2 states !Save reference orbitals on reforb1 !Dont use extra symmetries !MRCI at reference geometry !1B1 and 1A2 states !Use orbitals from previous CASSCF !Save MRCI wavefunction Text,Displaced geometries do i=1,#r data,truncate,savci+1 reforb=reforb1 do j=1,3 r2=r(i)+dr(j) {multi;occ,9,2;closed,4,1; wf,18,2,0;state,2; start,reforb orbital,3140.2+j; diab,reforb noextra} reforb=3141.2 {ci;occ,9,2;closed,4,1; wf,18,2,0;state,2; orbital,diabatic save,savci+j} eadia=energy if(j.eq.1) then e1(i)=energy(1) e2(i)=energy(2) end if {ci;trans,savci+j,savci+j; dm,7000.2+j} !Loop over different r values !truncate dumpfile after reference !Loop over small displacements for NACME !Set current r2 !Wavefunction definition !Starting orbitals !Dumprecord for orbitals !Generate diabatic orbitals relative to reference geometry !Dont use extra symmetries !Use orbitals for j=1 as reference for j=2,3 !Use diabatic orbitals !Save MRCI for displaced geometries !Save adiabatic energies for use in ddr !Save adiabatic energies for table printing !Compute transition densities at R2+DR(j) !Save transition densities on this record
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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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27 THE MRCC PROGRAM OF M. KALLAY (M
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28 SMILES 202 This code is not incl
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29 LOCAL CORRELATION TREATMENTS 204
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30 LOCAL METHODS FOR EXCITED STATES
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Page 261 and 262: 31 EXPLICITLY CORRELATED METHODS 22
Page 277 and 278: 32 THE FULL CI PROGRAM 244 32 THE F
Page 279 and 280: 33 SYMMETRY-ADAPTED INTERMOLECULAR
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
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Page 307 and 308: 38 QUASI-DIABATIZATION 274 This cal
Page 309: 38 QUASI-DIABATIZATION 276 ***,h2s
Page 313 and 314: 39 THE VB PROGRAM CASVB 280 39 THE
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Page 325 and 326: 40 SPIN-ORBIT-COUPLING 292 integral
Page 327 and 328: 40 SPIN-ORBIT-COUPLING 294 40.6.1 P
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Page 331 and 332: 41 ENERGY GRADIENTS 298 41 ENERGY G
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Page 335 and 336: 41 ENERGY GRADIENTS 302 ZMAT OPT3N
Page 337 and 338: 42 GEOMETRY OPTIMIZATION (OPTG) 304
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42 GEOMETRY OPTIMIZATION (OPTG) 328
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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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