diff --git a/doc/user/property.tex b/doc/user/property.tex index f113e930ef..29032298d9 100644 --- a/doc/user/property.tex +++ b/doc/user/property.tex @@ -1,80 +1,73 @@ % -% $Id: property.tex,v 1.23 2004-10-29 21:35:21 edo Exp $ +% $Id: property.tex,v 1.24 2004-12-20 20:00:30 bert Exp $ % \label{sec:property} + +Properties can be calculated for both the Hartree-Fock and DFT wave +functions. The properties that are available are: + +\begin{itemize} +\item Natural bond analysis +\item Dipole, quadrupole, and octupole moment +\item Mulliken population analysis and bond order analysis +\item Electrostatic potential (diamagnetic shielding) at nuclei +\item Electric field and field gradient at nuclei +\item Electron and spin density at nuclei +\item NMR shielding (GIAO method) +\item NMR hyperfine coupling (Fermi-Contact and Spin-Dipole expectation values) +\item NMR indirect spin-spin coupling +\end{itemize} + +The properties module is started when the task directive +\verb+TASK property+ is defined in the user input file. The input +format has the form: + \begin{verbatim} PROPERTY - [property name] + [property keyword] [CENTER ((com || coc || origin || arb ) default coc)] - [VECTORS ...] END \end{verbatim} -Calculation of properties is accomplished with \verb+TASK PROPERTY+ -after the completion of an energy (or MP2 gradient) calculation. The -following properties can be computed for all wavefunctions that produce -orbitals, including Hartree-Fock (closed-shell RHF, open-shell ROHF, and -open-shell UHF), DFT (closed-shell and open-shell spin unrestricted), -MCSCF (complete active space), and MP2 (closed-shell RHF and open-shell -UHF). +Most of the properties can be computed for Hartree-Fock +(closed-shell RHF, open-shell ROHF, and open-shell UHF), and DFT +(closed-shell and open-shell spin unrestricted) wavefunctions. The NMR +chemical shift is limited to closed-shell wave functions, whereas the NMR +hyperfine and indirect spin-spin coupling require a UHF or ODFT wave function. -\begin{itemize} -\item natural bond analysis -\item dipole moment -\item quadrupole moment -\item octupole moment -\item Mulliken population analysis and bond order analysis -\item electrostatic potential (diamagnetic shielding) at nuclei -\item electric field at nuclei -\item electric field gradient at nuclei -\item electron and spin density at nuclei -\item NMR chemical shifts (GIAO method) only for closed-shell RHF -\end{itemize} +\section{Property keywords} -The default molecular orbital file \verb+$file_prefix$.movecs+ is used -unless a vectors directive (Section \ref{sec:vectors}) is provided. It is -therefore only necessary to include a vectors directive if the MO vectors -to be analyzed are not coming from the default file, e.g., if they have -been previously redirected, or if MP2 natural orbitals (file extension -\verb+".mp2nos"+) are being anaylzed. The MP2 natural orbitals MUST be -used if the user wants MP2 properties. +Each property can be requested by defining one of the following keywords: -\section{Subdirectives} - -Note that presenting any property input causes all previous property input -to be ``forgotten'', unlike other NWChem modules. - -Each property can be requested by means of a subdirective among the -subdirectives provided : - -\begin{itemize} -\item {\tt NBOFILE} -\item {\tt DIPOLE} -\item {\tt QUADRUPOLE} -\item {\tt OCTUPOLE} -\item {\tt MULLIKEN} -\item {\tt ESP} -\item {\tt EFIELD} -\item {\tt EFIELDGRAD} -\item {\tt ELECTRONDENSITY} -\item {\tt GIAO} -\item {\tt ALL} -\end{itemize} +\begin{verbatim} + NBOFILE + DIPOLE + QUADRUPOLE + OCTUPOLE + MULLIKEN + ESP + EFIELD + EFIELDGRAD + ELECTRONDENSITY + HYPERFINE + SHIELDING [ number_of_atoms atom_list] + SPINSPIN [ number_of_pairs pair_list] + ALL +\end{verbatim} The ``{\tt ALL}'' keyword generates all currently available properties. -The request {\tt NBOFILE} does not execute the Natural Bond Analysis -code, but simply creates an input file to be used as input to the -stand-alone NBO code. All other properties are calculated upon -request. +Both the NMR shielding and spin-spin coupling have additional optional +parameters that can be defined in the input. For the shielding the user +can define the number of atoms for which the shielding tensor should be +calculated, followed by the list of specific atom centers. In the case +of spin-spin coupling the number of atom pairs, followed by the atom +pairs, can be defined (i.e., spinspin 1 1 2 will calculate the coupling +for one pair, and the coupling will be between atoms 1 and 2). -An additional subdirective is provided to specify the origin of the -molecular orbitals used in the calculation of the molecular -properties. This is the `{\tt VECTORS}' subdirective, also used in the -SCF and DFT tasks. For a full description of this subdirective -the user is refered to the description found in the SCF description. -By default, the input file used for the calculation of the properties -has the \verb+.movecs+ name extension. +For both the NMR spin-spin and hyperfine coupling the isotope that has +the highest abundance and has spin, will be choosen for each atom under +consideration. The user also has the option to choose the center of expansion for the dipole, quadrupole, and octupole calculations. @@ -92,14 +85,18 @@ must be given in the same units as \verb+UNITS+ in \verb+GEOMETRY+ (See Section \subsection{Nbofile} \label{sec:Nbofile} +The keyword {\tt NBOFILE} does not execute the Natural Bond Analysis +code, but simply creates an input file to be used as input to the +stand-alone NBO code. All other properties are calculated upon +request. + Following the successful completion of an electronic structure calculation, a Natural Bond Orbital (NBO) analysis may be carried out -in the following way. On restart specify the \verb+TASK+ as \verb+PROPERTY+ and -supply the sub-directive \verb+NBOFILE+ to the \verb+PROPERTY+ directive. NWChem -will query the rtdb and construct an ASCII file, +by providing the keyword \verb+NBOFILE+ in the \verb+PROPERTY+ directive. +NWChem will query the rtdb and construct an ASCII file, \verb+.gen+, that may be used as input to the stand alone version of the NBO program, gennbo. \verb++ is equal to -string following the \verb+RESTART+ directive. The input deck may be edited +string following the \verb+START+ directive. The input deck may be edited to provide additional options to the NBO calculation, (see the NBO user's manual for details.)