$LOCAL group (relevant if LOCAL=RUEDNBRG or BOYS) (relevant if LOCAL=POP or SVD) This group allows input of additional data to control the localization methods. If no input is provided, the valence orbitals will be localized as much as possible, while still leaving the wavefunction invariant. There are many specialized options for Localized Charge Distribution analysis, and for EFP generation. LOCAL=RUEDENBRG, BOYS, and POP all work by sequences of two by two Jacobi rotations. This needs iteration control, and permits fine tuning of the orbital pairs rotated, leading to keywords such as SYMLOC and MOIN/MOOUT below. LOCAL=SVD does a direct projection of the RHF, ROHF, or MCSCF orbitals onto the basis set of each atom, taking in turn atoms one by one, with a symmetric orthogonalization between atoms at the end. Consequently, many keywords here pertaining to iteration control and to various orbital restrictions (MOIN, MOOUT, SYMLOC, etc) don't pertain to LOCAL=SVD. N.B. Since Boys localization needs the dipole integrals, do not turn off dipole moment calculation in $ELMOM. MAXLOC = maximum number of localization cycles. This applies to BOYS or POP methods only. If the localization fails to converge, a different order of 2x2 pairwise rotations will be tried. (default=250) CVGLOC = convergence criterion. The default provides LMO coefficients accurate to 6 figures. (default=1.0E-6) SYMLOC = a flag to restrict localization so that orbitals of different symmetry types are not mixed. This option is not supported in all possible point groups. The purpose of this option is to give a better choice for the starting orbitals for GVB-PP or MCSCF runs, without destroying the orbital's symmetry. This option is compatible with each of the 3 methods of selecting the orbitals to be included. If chosen in a run requesting VVOS (see $SCF), occupied and virtual orbitals will also not be permitted to mix in a localization of these two separate orbital spaces. (default=.FALSE.) ORIENT = a flag to request orientation of the localized orbitals for bond-order analysis. After the localization, the orbitals on each atom are rotated only among themselves, in order to direct the orbitals towards neighboring atom's orbitals, to which they are bonded. The density matrix, or bond-order matrix, of these Oriented LMOs is readily interpreted as atomic populations and bond orders. This option can only be used for LOCAL=RUEDNBRG when SCFTYP=MCSCF, or if LOCAL=SVD. (default=.FALSE.) EXTLOC = options to localize external orbitals, above the valence MBS orbital space (SVD and ATMNOS), and to control internal orbital localization (SPLITxx keywords), in the valence minimal basis space. = NONE (default) = SVD Forms the SVD quasi-atomic external orbitals using an SVD with respect to the accurate atomic minimal basis functions. The localization of all internal orbitals means that ORMAS wavefunctions are not left invariant, nor are full spaces which are not full valence type. = ATMNOS Performs the EXTLOC=SVD option, and then forms the ordered external orbitals using exchange integrals. = SPLITQA Performs the EXTLOC=SVD and EXTLOC=ATMNOS options, and then, form split-localized orbitals in the internal orbital space, preserving ORMAS subspaces when doing the latter step. The next two skip localization in the external space, which saves time, for cases where only localization of internal orbitals is needed: = SPLITQ2 Forms the split-localized orbitals in the internal orbital space, preserving any ORMAS subspaces (wavefunction will be left invariant). = SPLITQ3 Forms the split-localized orbitals in the internal orbital space, but these split- localized orbitals do not preserve the ORMAS wavefunction. In other words, the split-localization treats the calculation as if it had a single united active space. PRTLOC = a flag to control supplemental printout. The extra output is the rotation matrix to the localized orbitals, and, for the Boys method, the orbital centroids, for the Ruedenberg method, the coulomb and exchange matrices, for the population method, atomic populations. (default=.FALSE.) ----- The following keywords select the orbitals which are to be included in the localization. You may select from FCORE, NOUTA/NOUTB, or NINA/NINB, but may choose only one of these three groups. These options do not pertain to LOCAL=SVD: FCORE = flag to freeze all the chemical core orbitals present. All the valence orbitals will be localized. You must explicitly turn this option off to choose one of the other two orbital selection options. (default=.TRUE.) * * * NOUTA = number of alpha orbitals to hold fixed in the localization. (default=0) MOOUTA = an array of NOUTA elements giving the numbers of the orbitals to hold fixed. For example, the input NOUTA=2 MOOUTA(1)=8,13 will freeze only orbitals 8 and 13. You must enter all the orbitals you want to freeze, including any cores. This variable has nothing to do with cows. NOUTB = number of beta orbitals to hold fixed in -UHF- localizations. (default=0) MOOUTB = same as MOOUTA, except that it applies to the beta orbitals, in -UHF- wavefunctions only. * * * NINA = number of alpha orbitals which are to be included in the localization. (default=0) MOINA = an array of NINA elements giving the numbers of the orbitals to be included in the localization. Any orbitals not mentioned will be frozen. NINB = number of -UHF- beta MOs in the localization. (default=0) MOINB = same as MOINA, except that it applies to the beta orbitals, in -UHF- wavefunctions only. ORMFUL = this flag is relevant only to CISTEP=ORMAS MCSCF localizations. By default, the localization is restricted such that the multiple active spaces are not mixed, leaving the total wavefunction invariant. It may be used to localize within the full range of active MOs. (Default is .FALSE.) ----- The following keywords are used for the localized charge distribution (LCD), a decomposition scheme for the energy, or multipole moments, or the first polarizability. See also LOCHYP in $FFCALC for the decomposition of hyperpolarizabilities. EDCOMP = flag to turn on LCD energy decomposition. Note that this method is currently implemented for SCFTYP=RHF and ROHF and LOCAL=RUEDNBRG only. The SCF LCD forces all orbitals to be localized, overriding input on the previous page. See also LMOMP2 in the $MP2 input. (default = .FALSE.) MOIDON = flag to turn on LMO identification and subsequent LMO reordering, and assign nuclear LCD automat- ically. (default = .FALSE.) DIPDCM = flag for LCD molecular dipole decomposition. (default = .FALSE.) QADDCM = flag for LCD molecular quadrupole decomposition. (default = .FALSE.) POLDCM = flag to compute the static alpha polarizability, and its decomposition in terms of LCDs. LMO dipole polarizabilities are the polarizability term in the EFP model. The computation is done analytically, for SCFTYP of RHF or ROHF, but must be done numerically for their DFT counterparts (choose one of POLNUM or POLAPP). No other correlation method makes sense, since the point of this keyword is a decomposition over localized orbitals. LOCAL may be BOYS or RUEDNBRG. See also LOCHYP in $FFCALC for a similar breakdown of static beta and gamma hyperpolarizabilities. Default=.FALSE., except that RUNTYP=MAKEFP turns this computation on, automatically. POLNUM = flag to force numerical rather than analytical calculation of the polarizabilities. This may be much faster for larger molecules. The numerical polarizabilities of bonds in or around aromatic rings sometimes are unphysical. (default=.FALSE.) See D.R.Garmer, W.J.Stevens J.Phys.Chem. 93, 8263-8270(1989). This keyword cannot be used with POLDYN or POLAPP. POLAPP = flag to force calculation of the polarizabilities using a perturbation theory expression. This may be useful in larger molecules. (default=.FALSE.) See R.M. Minikis, V. Kairys, J.H. Jensen J.Phys.Chem.A 105, 3829-3837(2001) Quality of the results is not as good as POLNUM! This keyword cannot be used with POLDYN or POLNUM. POLANG = flag to choose units of localized polarizability output. The default is Angstroms**3, while false will give Bohr**3. (default=.TRUE.) ZDO = flag for LCD analysis of a composite wavefunction, given in a $VEC input of a van der Waals complex, using the zero differential overlap approximation. The MOs are not orthonormalized and the inter- molecular electron exchange energy is neglected. Also, the molecular overlap matrix is printed out. This is a very specialized option. (default = .FALSE.) ----- The following keywords can be used to define the nuclear part of an LCD. They are usually used to rectify mistakes in the automatic definition made when MOIDON=.TRUE. The index defining the LMO number then refers to the reordered list of LMOs. NMOIJ = array giving the number of nuclei assigned to a particular LMO. IJMO = is an array of pairs of indices (I,J), giving the row (nucleus I) and column (orbital J) index of the entries in ZIJ and MOIJ. MOIJ = arrays of integers K, assigning nucleus K as the site of the Ith charge of LCD J. ZIJ = array of floating point numbers assigning a charge to the Ith charge of LCD J. IPROT = array of integers K, defining nucleus K as a proton. DEPRNT = a flag for additional decomposition printing, such as pair contributions to various energy terms, and centroids of the Ruedenberg orbitals. (default = .FALSE.) ----- The following keywords are used to build large EFPs from several RUNTYP=MAKEFP runs on smaller molecular fragments, by excluding common regions of overlap. For example, an EFP for n-octanol can be build from two MAKEFP runs, on n-pentane and n-pentanol, CH3CH2CH2CH2-CH2CH2CH2CH2OH CH3CH2CH2CH2[-CH3] [CH3]-CH2CH2CH2CH2OH by excluding operlapping regions shown in brackets from the two EFPs. See J.Phys.Chem.A 105, 3829-3837, (2001) for more information. NOPATM = array of atoms that define an area to be excluded from a DMA ($STONE) during a RUNTYP=MAKEFP run. All atomic centers specified, and the midpoints of any bonds to them, are excluded as expansion points. The density due to all LMOs primarily centered on these atoms are excluded from the DMA (see also KMIDPT). Furthermore, polarizability tensors for these LMOs are excluded. KPOINT = array of "boundary atoms", those atoms that are covalently bonded to the atoms given in NOATM. KMIDPT = flag to indicate whether the density due to bond LMOs (and associated expansion points) between the NOPATM atoms and the KPOINT atoms are to be included in the DMA. (default = .TRUE.) NODENS = an array that specifies the atoms for which the associated electronic density will be removed before the multipole expansion. This provides an EFP with net integer charge. (P.A.Molina, H.Li, J.H.Jensen J.Comput.Chem. 24, 1972-1979(2003). The following keywords relate to the computation of imaginary frequency dynamic polarizabilities. This is useful in the development of the dispersion energy formula in the EFP2 model, but may also be computed separately, if wished. POLDYN = a flag to compute imaginary frequency dependent dynamic polarizabilities (alpha), by analytic means. Available only for uncorrelated RHF. (default=.FALSE., but .TRUE. if RUNTYP=MAKEFP) NDPFRQ = number of imaginary frequencies to compute. Default=1 for most runs, but=12 if RUNTYP=MAKEFP. DPFREQ = an array of imaginary frequencies to be used, entered as real numbers (absolute values). The default=0.0 for most runs, which is silly, because this just computes the normal static dipole polarizability! For RUNTYP=MAKEFP, the program uses 12 internally stored values, which serve as the roots for a Gauss-Legendre quadrature to extract the C6 dispersion coefficients. Given in atomic units. For more information, see I.Adamovic, M.S.Gordon Mol.Phys. 103, 379-387(2005). ========================================================== * * * * * * * * * * * * * * * * * * For hints about localizations, and the LCD energy decomposition, see the 'further information' section. * * * * * * * * * * * * * * * * * * ==========================================================

generated on 7/7/2017