https://www.molpro.net/manual/ 2026-04-29T13:13:13+00:00 https://www.molpro.net/manual/ https://www.molpro.net/manual/lib/exe/fetch.php?media=logo.png text/html 2025-04-14T07:06:15+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=ab_initio_multiple_spawning_dynamics&rev=1744614375&do=diff Ab initio multiple spawning dynamics (AIMS) AIMS is a multi-state first-principles dynamics program written by Benjamin G. Levine, Joshua D. Coe, Aaron M. Virshup, Hongli Tao, Christian R. Evenhuis, William J. Glover, Toshifumi Mori, Michal Ben-Nun and Todd J. Martinez.$\pm 0.5\times$$\langle r^2 \rangle$$\vdots$$\vdots$$\vdots$$\neq$$^{-1}$$\langle r^2 \rangle$$\langle \Psi(t) | \Psi(0) \rangle$ text/html 2025-09-19T09:14:42+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=automated_construction_of_atomic_valence_active_spaces&rev=1758273282&do=diff Automated construction of atomic valence active spaces (AVAS) Atomic valence active spaces (AVAS) as described by Knizia et al. can be generated using the AVAS program. AVAS can be used in two different modes: either as an independent program, or within the Hartree-Fock program using the converged orbitals. The default behaviour in both cases differs slightly, as described below.$n$$n-l$$s$$p$$d$$n$$n$$n$ text/html 2025-09-12T09:08:01+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=basis_input&rev=1757668081&do=diff Basis input Overview: sets and the basis library Basis functions are used in Molpro not just for representing orbitals, but also for providing auxiliary sets for density fitting (see density fitting) and for simplifying integrals through approximate identity resolution in explicitly-correlated methods (see $5d$$7f$$_2$$f$$g$$1$$d$$s$$p$$d$$|$$|$$|nprim|$$ndel$$\ldots$$\ldots$$n$$c$$r$$d$$r$$r=2.5$$d=1$$$\log e_i = \log c + ((n+1)/2-i) \,\log r + \frac12 ((n+1)/2-i)^2 \,\log d \quad i=1,2,\dots… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=basis_set_extrapolation&rev=1720773475&do=diff Basis set extrapolation Basis set extrapolation can be carried out for correlation consistent basis sets using EXTRAPOLATE,BASIS=basislist,options where basislist is a list of at least two basis sets separated by colons, e.g. AVTZ:AVQZ:AV5Z. Some extrapolation types need three or more basis sets, others only two. The default is to use $n^{-3}$$p$$p$$n$$x$$p$$p=0$$nx$$A$$B$$A_i$$E_{n} = E_{\tt CBS} + A \cdot (n+p)^{-x}$$E_{n} = E_{\tt CBS} + A \cdot (n+\frac{1}{2})^{-x}$$E_{n} = E_{\tt CBS} + … text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=chemical_shieldings_magnetizability_and_rotational_g-tensor&rev=1720773475&do=diff Chemical shieldings, magnetizability, and rotational g-tensor Bibliography: $[1]$ S. Loibl, F.R. Manby, M. Schütz, Density fitted, local Hartree-Fock treatment of NMR chemical shifts using London atomic orbitals, Mol. Phys. 108, 477 (2010). $[2]$ S. Loibl and M. Schütz, $[3]$$\sigma$$g$$g$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=core_polarization_potentials&rev=1720773475&do=diff Core polarization potentials Input options The calculation of core-polarization matrix elements is invoked by the CPP card, which can be called at an arbitrary position in the MOLPRO input, provided the usual AO integrals have been calculated before. The CPP card can have the following formats:$<ncentres>$$<ncentres>$$<atomtype>,<ntype>,<\alpha_d>,<\alpha_q>,<\beta_d>,<cutoff>,<q_{eff}$$<atomtype>$$<ntype>$$<\alpha_d>$$<\alpha_q>$$<\beta_d>$$<cutoff>$$<q_{eff}$$<ncentres>$$h_0$$<factor>$$<fact… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=definition_of_molpro_input_language&rev=1720773475&do=diff Definition of Molpro input language Input format Molpro’s execution is controlled by an input file. In general, each input record begins with a keyword, which may be followed by data or other keywords. Molpro input contains commands, directives, options and data. The commands and directives are sequentially executed in the order they are encountered. Furthermore, procedures can be defined anywhere in the input, which can include any number of commands and directives. They are only executed whe… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=density_fitting&rev=1720773475&do=diff Density fitting Density fitting can be used to approximate the integrals in spin restricted Hartree-Fock (HF), density functional theory (KS), second-order Møller-Plesset perturbation theory (MP2 and RMP2), explicitly correlated MP2 (MP2-F12), all levels of closed-shell local correlation methods ( text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=density_functional_descriptions&rev=1720773475&do=diff Density functional descriptions B86: Xalpha beta gamma Divergence free semiempirical gradient-corrected exchange energy functional. $\lambda=\gamma$ in ref. $$g=-{\frac {c \left( \rho \left( s \right) \right) ^{4/3} \left( 1+ \beta\, \left( \chi \left( s \right) \right) ^{2} \right) }{1+\lambda \, \left( \chi \left( s \right) \right) ^{2}}} ,$$ $$G=-{\frac {c \left( \rho \left( s \right) \right) ^{4/3} \left( 1+ \beta\, \left( \chi \left( s \right) \right) ^{2} \right) }{1+\lambda \, \le… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=dump_density_or_orbital_values_cube&rev=1720773475&do=diff Dump density or orbital values (CUBE) CUBE,filename,iflag,$n_1$,$n_2$,$n_3$ calls a module which dumps the values of various properties on a spatial parallelopipedal grid to an external file. The purpose is to allow plotting of orbitals, densities and other quantities by external programs. The format of the file is intended to be the same as that produced by other programs.$x$$z$$n_1$$n_2$$n_3$$n_1 \times n_2$$n_3$$n_3$$z$$n_1$$x$$m$$3n_3$ text/html 2024-10-25T16:06:26+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=effective_core_potentials&rev=1729872386&do=diff Effective core potentials Pseudopotentials (effective core potentials, ECPs) may be defined at the beginning of BASIS blocks. The general form of the input cards is ECP,atom,[ECP specification] which defines a pseudopotential for an atom specified either by a chemical symbol or a group number. The $e^-$$e^-$$3s$$3p$$nXY$$n$$X$$X=S$$X=M$$Y$$Y=HF$$Y=WB$$Y=DF$$X=S$$Y=DF$$X=M$$Y=WB$$Y=DF$$Y=HF$$n_{core},l_{max},l'_{max}$$n_{core}$$V_{ps}$$l_{max}$$V_{ps}$$l'_{max}$$$V_{ps}= -\frac{Z-n_{core}}{r}… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=energy_gradients&rev=1720773475&do=diff Energy gradients Analytical energy gradients Molpro uses different gradient programs: The Cadpac gradient program is based on the Cadpac integral routines by R. D. Amos. Currently, this program works for closed shell SCF, high spin RHF, and (state averaged) MCSCF. In the MCSCF case the wavefunction must either be fully optimized, or frozen core orbitals must be taken from a closed-shell SCF calculation (but this does not work in the case of state-averaged MCSCF). Note that $^2\Pi$$^2\Sigma^+$… text/html 2025-07-19T19:12:35+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=excited_states_with_equation-of-motion_ccsd_eom-ccsd&rev=1752952355&do=diff Excited states with equation-of-motion CCSD (EOM-CCSD) Excitation energies for singlet states can be computed using equation-of-motion (EOM) approach. For the excitation energies the EOM-CCSD method gives the same results as linear response CCSD (LR-CCSD) theory. Accurate results can only be expected for excited states dominated by single excitations. The states to be computed are specified on an $n1$$n2$$n1$$n2$$-3.1$$2.2$$2.3$$-5.3$$x$$n$$n$$nmax=ns+nd$$[1]$$[2]$$[3]$$[4]$$[5]$${\cal O}(W^3)$… text/html 2025-05-26T15:02:08+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=explicitly_correlated_methods&rev=1748271728&do=diff Explicitly correlated methods Explicitly correlated calculations provide a dramatic improvement of the basis set convergence of MP2, CCSD, CASPT2, and MRCI correlation energies. Such calculations can be performed using the commands of the form command$$\begin{aligned} \hat Q_{12} &=& (1-\hat o_1) (1 - \hat o_2) (1 - \hat v_1 \hat v_2),\nonumber\end{aligned}$$$\hat o_i$$i$$\hat v_i$$\hat v$$\hat d^{ij}$$ij$\begin{align} |u_{ijp}^{\rm F12}\rangle &=& \sum_{p=\pm 1} \sum_{kl} T^{ijp}_{kl} \ha… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=file_handling&rev=1720773475&do=diff File handling FILE The FILE directive is used to open permanent files, which can be used for later restarts. The file name must not contain parenthesis, brackets, exclamation marks, or other special characters like exclamation marks (!), question marks (?), slashes (/), backslashes (\), blanks( ), equality signs($=$$\ldots$$3 \cdot$$1 \le.$$\le.3$ text/html 2025-02-07T13:01:53+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=franck-condon_calculations&rev=1738933313&do=diff Franck-Condon calculations FRANCK-CONDON FACTORS (FCON) FCON,options [fcon] The FCON program allows for the calculation of Franck-Condon factors based on potential energy surfaces obtained from the XSURF program and vibrational wavefunctions as provided by the $\delta$$\leq$$\sim 10-10000$ text/html 2025-01-15T16:40:05+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=ga_installation&rev=1736959205&do=diff GA Installation We recommend building Molpro with the Global Arrays toolkit, using the latest stable version. There are different ways (GA “runtimes”) to configure the GA library which significantly affect the execution and options, and they are therefore important from a users point of view. The current default of the GA installation is to use text/html 2025-07-15T11:08:26+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=general_hints_-_frequently_asked_questions&rev=1752577706&do=diff General hints - frequently asked questions Molpro users should have a basic knowledge of quantum chemistry, from text books as recommended below. Also, a basic knowledge of Linux / macOS is required. As an introduction, studying the examples in this manual is recommended. Also, the Molpro forum at text/html 2025-08-28T12:30:41+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=general_program_structure&rev=1756384241&do=diff General program structure This chapter gives an overview of the most important features of Molpro. For the new user, it is essential to understand the strategies and conventions described in this section, in particular the meaning of files and records$\le$$32000000$$0|1$$10^3$$10^6$$10^9$$10^9$$|$$10^9$$2^{10}$$2^{20}$$2^{30}$$10^9$$2^{30}$$100 * 10^6$$100 * 10^6 * 8 * 4 = 3.2 * 10^9$$C_{2v}$$D_{2h}$$x$$y$$z$$z$$C_2$$C_{2h}$$C_1$$C_s$$C_2$$C_i$$C_{2v}$$C_{2h}$$D_2$$D_{2h}$$x$$y$$z$$s$$s$$x^2$$y… text/html 2025-09-29T09:05:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=geometry_optimization_optg&rev=1759136755&do=diff Geometry optimization (OPTG) Automatic geometry optimization is invoked using the OPTG command. The OPT command available in previous MOLPRO versions is no longer needed and not available any more. OPTG[, key1=value, key2=value,…...] The OPTG command can be used to perform automatic geometry optimizations for all kinds of wavefunctions. For minimum searches, it is usually sufficient to give just the $6^{-1/2}(R_{IJ} - R_{JK} + 2 A_{IJK})$$3 \cdot 10^{-4}$$1 \cdot 10^{-6}$$3 \cdot 10^{-4}$$3 \… text/html 2025-08-28T14:13:44+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=gmolpro_graphical_user_interface&rev=1756390424&do=diff gmolpro graphical user interface gmolpro is a GTK-based graphical interface to Molpro that runs on Linux and macOS workstations. Basic Molpro inputs can be very quickly generated. Sensible basis sets and input parameters are suggested. The preparation of inputs is supported through an expert system that interacts with Molpro’s registry of commands, methods, and basis sets, guiding the user toward feasible combinations of calculation types (single point, optimization, etc.), methods, basis set… text/html 2025-03-13T10:30:44+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=harmonic_vibrational_frequencies_frequencies&rev=1741861844&do=diff Harmonic vibrational frequencies (FREQUENCIES) FREQUENCIES,options, [forces:frequencies] Calculate harmonic vibrational frequencies and normal modes. For the calculation of anharmonic vibrational frequencies see sections POTENTIAL ENERGY SURFACES (SURF) to vibration correlation programs. The hessian is calculated analytically or numerically by finite differences in 3N cartesian coordinates (Z-Matrix coordinates will be destroyed on entry). If analytic gradients are available these are differen… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=how_to_read_this_manual&rev=1720773475&do=diff How to read this manual This manual is organized as follows: The next chapter gives an overview of the general structure of Molpro . It is essential for the new user to read this chapter, in order to understand the conventions used to define the symmetry, records and files, orbital spaces and so on. The later chapters, which describe the input of the individual program modules in detail, assume that you are familiar with these concepts. The appendices describe details of running the program, an… text/html 2024-08-21T22:24:40+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=index&rev=1724279080&do=diff Index * --- link link * *** link * 2nd Order Vibrational Perturbation Theory link * ACCURACY link link * ACPF link * ACTIVE link * ADD link link link link * AIMS link * ALTERN link * ANGULAR link * AOINT link * AQCC link * arrays link * ASYMP link * Atomic mass link * AVAS link * basis * cartesian text/html 2025-10-21T19:13:04+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=installation_guide&rev=1761073984&do=diff Installation guide Molpro is distributed to licensees on a self-service basis using the world-wide web. Those entitled to the code should obtain it from <https://www.molpro.net/download> supplying the username and password given to them. The web pages contain links to the binaries and source code, although not everyone is entitled to source code, and binaries are not available for every platform. text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=instantons&rev=1720773475&do=diff Instantons Instantons can be located within the ring-polymer formalism using the INSTANTON command: INSTANTON[, key1=value, key2=value, …] These instantons can be used to compute either the thermal reaction rate or the tunnelling splitting between degenerate potential wells. The behaviour can be controlled with the $N$$\beta$$\beta/N$$\beta_{\text{c}}=2\pi/\hbar\omega_{\text{b}}$$\mathrm{i}\omega_{\text{b}}$$B_N$$n$$n-1$$\beta\rightarrow\infty$$\beta/N\rightarrow0$$N/2$$N$$N$$T$$\beta$$E_{\te… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=integration&rev=1720773475&do=diff Integration Before starting any energy calculations, the geometry and basis set must be defined in GEOMETRY and BASIS blocks, respectively. By default, two electron integrals are evaluated once and stored on disk. This behaviour may be overridden by using the input command $\dots$$0.0$$\ge 0$$\lt 0$$\lt -1$$\lt -2$${\tt SCREEN}$$-1$$\geq 0$$= -1$$= -2$$= -1$$= -1$$= -2$$(\mu \mu | \nu \nu)$${\tt SCREEN}$$\ge 1$$1$$7$$1$$-1$$1$$32$$0$$16$$-1$$3$$0$$5$$1$$-1$$\min(\Delta E \cdot 1.d-2,1.d-9)^{a,b… text/html 2025-07-18T08:18:22+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=intermolecular_interaction_energies&rev=1752826702&do=diff Intermolecular interaction energies Counterpoise corrected (or uncorrected) intermolecular interaction energies can be computed automatically using the INTERACT procedure: INTERACT, options The INTERACT command can follow any input for a complete energy calculation and then computes the interaction energy for the last computed energy method. Alternatively, the energy calculation can be defined in a procedure. In this case, the procedure must contain input for a complete energy calculation, in… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=internally_contracted_multireference_coupled-cluster_theory&rev=1720773475&do=diff Multireference CC computations Internally contracted multireference internally contracted coupled-cluster theory Bibliography: M. Hanauer, A. Köhn, J. Chem. Phys. 134, 204111 (2011). A. Köhn, J. A. Black, Y. A. Aoto, M. Hanauer, Mol. Phys. 118, e1743889 (2020). A. Waigum, J. A. Black, A. Köhn, text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=intrinsic_basis_bonding_analysis_iao_ibo&rev=1720773475&do=diff Intrinsic basis bonding analysis (IAO/IBO) The IBBA program is used to perform a chemical bonding analysis of a previously computed Hartree-Fock or Kohn-Sham wave function. Options include the computation of partial charges, bond orders, and localized bond orbitals (i.e., orbitals which correspond to “chemical intuition” bonds). The localized orbitals can be visualized by exporting to $\rightarrow$$\rightarrow$$\vert\mathrm{IAO}\rangle=(1+o-\tilde o)P_{12}\vert\mathrm{minao}\rangle$$\vert\mathr… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=introduction_to_molpro&rev=1720773475&do=diff Introduction to Molpro Molpro is a complete system of ab initio programs for molecular electronic structure calculations, designed and maintained by H.-J. Werner and P. J. Knowles, and containing contributions from a number of other authors. As distinct from other commonly used quantum chemistry packages, the emphasis is on highly accurate computations, with extensive treatment of the electron correlation problem through the multiconfiguration-reference CI, coupled cluster and associated method… text/html 2025-10-14T07:46:29+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=introductory_examples&rev=1760427989&do=diff Introductory examples This section explains some very simple calculations in order to help the new user to understand how easy things can be. Using the molpro command Perform a simple SCF calculation for molecular hydrogen. The input is typed in directly and the output is sent to the terminal:$_2$$f$$d$$\rm H_2O$ text/html 2025-07-30T22:26:15+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=kohn-sham_random-phase_approximation&rev=1753914375&do=diff Kohn-Sham random-phase approximation This chapter describes three different programs that are related to Kohn-Sham based RPA correlation methods. The first one is the density fitting RPA program of Heßelmann et al. described in section Density fitting RPA programs. The second one is the $[1]$$[2]$$[3]$$[4]$$T^{\text{new}}=f T^{\text{old}}+(1-f)T^{\text{new}}$$N_{\text{aux}}\times N_{\text{virt}}$$N_{\text{aux}}$$N_{\text{virt}}$$\ne$$\ne$$\ne 0$$\epsilon$$f=1-\rho/(\rho+\epsilon)$$s$$\rho=\rho+… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=license_information&rev=1720773475&do=diff License information The Molpro source code contains some external code which is listed in this section. Molpro binaries may, in some instances, contain compiled versions of this code also. Eigen The Eigen template library is included when Molpro is compiled. Eigen is licensed under the text/html 2025-10-25T07:14:36+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=local_correlation_methods_with_pair_natural_orbitals_pnos&rev=1761376476&do=diff Local correlation methods with pair natural orbitals (PNOs) In this page single-reference local correlation methods using pair natural orbitals (PNOs) are described. This program is entirely distinct from the older PAO-based methods. It is designed for parallel execution both on one node and across multiple nodes. By default, the program store some data in distributed memory, which means more memory is required than in other programs. The memory required per CPU core for these distributed data … text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=local_methods_for_excited_states&rev=1720773475&do=diff Local methods for excited states Local CC2 and ADC(2) Bibliography: General local CC2 for excited states: $[1]$ D. Kats, T. Korona and M. Schütz, Local CC2 electronic excitation energies for large molecules with density fitting, J. Chem. Phys. 125, 104106 (2006). $[2]$$[3]$$[4]$$[5]$$[6]$$7]$$8]$$[9]$$=1$$=1$$[ij]\leq$$[im]\leq$$[mn]\leq$$\forall [ij]$$\forall [im]$$[mn]\leq$$\forall [ij]$$[im]\leq$$[mn]\leq$$i$$j$$m$$n$$(H-F)^{\rm CIS}$$(H-F)^{\rm CIS}$$\Longrightarrow$$\geq 0$$\leq 0$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=matrix_operations&rev=1720773475&do=diff Matrix operations MATROP; MATROP performs simple matrix manipulations for matrices whose dimensions are those of the one particle basis set. To do so, first required matrices are loaded into memory using the LOAD command. To each matrix an internal ${\bf S}^{-1/2}$$np=1,0,-1$$result(a,b)=result(a,b) + factor*v1(a)*v2(b)$$i$$n_1,n_2,n_3,\ldots,n_8$$n_i$$i$$n_i=0$$_2$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=minimization_of_functions&rev=1720773475&do=diff Minimization of functions The minimization of general functions of one or more variables can be carried out using the command: MINIMIZE, func, x$_1$[, x$_2$, x$_3$, …] where func represents a function of up to 50 variables x$_1$, x$_2$, …. Two different optimization methods can be selected as described below which do or do not use numerical derivative information.$x$$x_1/x_{1i}$$1 \cdot 10^{-4}$$1 \cdot 10^{-2}$ text/html 2025-07-21T09:03:49+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=molecular_geometry&rev=1753088629&do=diff Molecular geometry Geometry specifications The geometry may be given in standard Z-matrix form, or XYZ form, either in the input or in a separate file (see section geometry files). The geometry specifications are given in the form [SYMMETRY, options ] [ORIENT, options $x$$y$$z$$C_{2v}$$D_{2h}$$xz$$yz$$5a$$5b$$C_{2v}$$p_1$$r$$p_2$$\alpha$$p_3$$\beta$$J$$p_1$$x$$y$$z$$p_0$$n$$n$$p_1$$\alpha(p_0,p_1,p_2)$$p_1$$\alpha(p_0,p_1,p_2)$$0 \lt \alpha \lt 180^{0}$$\beta(p_0,p_1,p_2,p_3)$$J=0$$\beta(p_0… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=moller_plesset_perturbation_theory&rev=1720773475&do=diff Møller Plesset perturbation theory Closed-shell Møller-Plesset perturbation theory up to full fourth order [MP4(SDTQ)] is part of the coupled-cluster program. The commands MP2, MP3, MP4 perform the MP calculations up to the specified order (lower orders are included). text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=molpro_on_the_www&rev=1720773475&do=diff Molpro on the www The latest information on Molpro, including program updates, can be found here. text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=multireference_local_correlation_methods_pno-caspt2&rev=1720773475&do=diff Multireference local correlation methods (PNO-CASPT2) In this section multireference local correlation methods are described. Many keywords are similar to PNO-based single-reference methods and RS2 methods. Especially pre-allocating GA memory might be required for large calculations as described in $f^c$\begin{equation} H_{MN}^\textrm{eff}=\frac{1}{2}\left( \langle M|\hat H ~^N\hat T_2|N\rangle + \langle M | ~^… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=multireference_rayleigh_schroedinger_perturbation_theory&rev=1720773475&do=diff Multireference Rayleigh Schrödinger perturbation theory Bibliography: * Original RS2/RS3: H.-J. Werner, Mol. Phys. 89, 645-661 (1996) * New internally contracted RS2C: P. Celani and H.-J. Werner, J. Chem. Phys. 112, 5546 (2000) All publications resulting from use of this program must acknowledge the above.$(\hat H^{(0)} - E^{(0)})$$istate$$istate=2,\ldots,nstates$$B_1$$g_1$$g_2$$g_3$$g_4$$g_4$$n$$n$$0.1 - 0.3$$\frac{1}{2} D_{pp} \epsilon$$2 \epsilon$$\epsilon$$n$$n$$n$$\hat H^{(0)}$$1 \le… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=non_adiabatic_coupling_matrix_elements&rev=1720773475&do=diff Non adiabatic coupling matrix elements Non-adiabatic coupling matrix elements can be computed by finite differences for MCSCF or CI wavefunctions using the DDR program. For state-averaged MCSCF wavefunctions, they can also be computed analytically (cf. section $\gamma(R|R)$$\gamma(R|R+DR)$$\gamma(R|R-DR)$ text/html 2025-05-21T12:36:39+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=nuclear-electronic_orbital_method&rev=1747830999&do=diff Nuclear-electronic orbital (NEO) method The Nuclear-electron orbital (NEO) method pioneered by Hammes-Schiffer and coworkers is available in Molpro for (local) density fitted spin-restricted NEO-Hartree-Fock as well as NEO-RKS. It allows to handle a selected number of hydrogen nuclei as quantum particles by building a second Fock-matrix for the latter, coupling both subsystems (electrons and quantum protons) by a Coulomb operator. Further information about the method can be found text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=open-shell_coupled_cluster_theories&rev=1720773475&do=diff Open-shell coupled cluster theories Spin unrestricted (RHF-UCCSD) and partially spin restricted (RHF-RCCSD) open-shell coupled cluster theories as described in J. Chem. Phys. 99, 5219 (1993) (see also erratum, J. Chem. Phys. 112, 3106 (2000)) are available in Molpro. In both cases a high-spin $X^{ijk}_{abc}$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=orbital_localization&rev=1720773475&do=diff Orbital localization Localized orbitals are calculated according to the Boys, Pipek-Mezey or NLMO criteria. Localization takes place within each symmetry species separately. For intrisnic bond orbital (IBO) localization, see the IBBA program, section $o_1$$o_2 \ldots$$o_i$$i$$c_1$$c_2 \ldots$$c_i$$c_i+1$$o_i$$i$$>$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=orbital_merging&rev=1720773475&do=diff Orbital merging Orbitals can be manipulated using the MERGE facility. For instance, this allows the construction of molecular orbitals from atomic orbitals, to merge and orthogonalize different orbital sets, or to perform $2 \times 2$ rotations between individual orbitals. Other orbital manipulations can be performed using the $n_1,n_2,\ldots,n_8$$n_i$$i$$n_1,n_2,\ldots,n_8$$n_i$$i$$2 \times 2$$_2$$_{2v}$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=pao-based_local_correlation_treatments&rev=1720773475&do=diff PAO-based local correlation treatments Introduction In this section the original PAO-based local correlation methods are described. Since Molpro version 2018, a completely new PNO-LCCSD(T)-F12 program is available, which is much more accurate and well parallelized. It is recommended to use this new program, which is described in section $[1]$$[2]$$[3]$$[4]$$[5]$$[6]$$[7]$$[8]$$[9]$$[10]$$[11]$$[12]$$[13]$$[14]$$[15]$$[16]$$[17]$$[18]$$[19]$$[20]$$[21]$$[22]$$[23]$$[24]$$[25]$$\gt 0$$\gt 1$$\le… text/html 2025-05-22T10:32:19+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=pes_generators&rev=1747909939&do=diff PES generators POTENTIAL ENERGY SURFACES (XSURF) {XSURF,options} The XSURF program allows for the calculation of the potential energy surface around a reference structure as required for the calculation of anharmonic frequencies (see the VSCF, VCI$n$$$V(q_1,\dots,q_{3N-6}) = \sum_i V_i(q_i) + \sum_{i<j} V_{ij}(q_i,q_j) + \sum_{i<j<k} V_{ijk}(q_i,q_j,q_k) + \dots$$$$\begin{eqnarray*} V_i(q_i) & = & V_i^0(q_i) - V(0) \\ V_{ij}(q_i,q_j) & = & V_{ij}^0(q_i,q_j) - \sum_{r\in\{i,j\}} V_r(q_r) - V(… text/html 2025-05-22T09:29:07+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=pes_transformations&rev=1747906147&do=diff PES transformations Once a potential energy surface (PES) has been generated by the XSURF program, it can be transformed to different representations. The first possibility (analytical representations (POLY)) is a representation by basis functions, i.e. the POLY program. The PESTRANS$\chi^2$$\chi^2$$n$$n$$n$$n$$n$$\mu$$x$$n$$n$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=physical_constants&rev=1720773475&do=diff Physical constants The values of fundamental physical constants are revised periodically by CODATA. Molpro uses the values from the latest revision. Some previous values are available, see the lib/include/codata/ directory. To use these system include files, simply add for instance: text/html 2025-03-12T09:38:21+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=post-processing_of_output_and_databases&rev=1741772301&do=diff Post-processing of output and databases Output Molpro produces an output file that is in XML format with appropriate mark-up for all important results. This file, which has a .xml suffix, conforms strictly to a well-defined schema, and the the schema definition file can be found in the main Molpro source or installation tree in the directory text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=processing_and_plotting_for_rovibrational_line_lists_dat2gr&rev=1720773475&do=diff Processing and plotting for rovibrational line lists (DAT2GR) The DAT2GR program is used to process and to generate plots from rovibrational infrared and Raman line lists generated by the RCI and RVCI programs that are part of the VSCF and VCI progam.$T=0$$R_0$$R_2$$\sigma$$\gamma$$^{-1}$$^{-1}$$^{-1}$$\gamma$$^{-1}$$\sigma$$n=0$$R_0$$n=2$$R_2$$^{-1}$$^{-1}$$\{0.5,1.0,2.0\}$$^{-1}$$\{5,50,150,295\}$$R_0$$R_2$$90^\circ$$514$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=processing_and_plotting_rovibrational_line_lists_dat2gr&rev=1720773475&do=diff Processing and plotting for rovibrational line lists (DAT2GR) The DAT2GR program is intented to be used to read in rovibrational line lists of infrared and Raman spectra, generated by the RCI and RVCI extension of the VSCF and VCI program. text/html 2025-04-24T10:59:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=processing_of_rovibrational_line_lists_dat2gr&rev=1745492395&do=diff Processing of rovibrational line lists (DAT2GR) The DAT2GR program is used to process and to generate plots from rovibrational infrared and Raman line lists generated by the RVCI program that is part of the VCI program. The DAT2GR program (DAT2GR) $^{-1}$$^{-1}$$^{-1}$$^{-1}$$\gamma = \frac{p A}{\pi c} \sqrt{\frac{2}{k_B T m}} $$p$$A$$c$$k_B$$T$$m$$T=0$$R_0$$R_2$$\sigma$$\gamma$$n=0$$R_0$$n=2$$R_2$$^{-1}$$^{-1}$$\sigma = \frac{1}{c} \sqrt{\frac{8 k_B T ln(2)}{m}} $$c$$k_B$$T$$m$$^{-1}$ text/html 2025-10-27T06:52:54+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=program_control&rev=1761547974&do=diff Program control Starting a job (***) The first card of each input should be: ***,text where text is arbitrary. If file 1 is restarted, text must always be the same. The effect of this card is to reset all program counters, etc. If the *** card is omitted, $r_1,r_2,r_3,r_4,\ldots$$r_i$$r_i$$r_i$$nr$$r_i=0$$r_i$$n$$|n|$$n=1$$n \lt 0$$\{$$_2$$>0$$\gt 0$$\gt$$=0$$\Delta^4$$n$$R^2$$\hat L_x$$\hat L_y$$\hat L_z$$\frac{1}{2} (\hat L_x \hat L_y+\hat L_y \hat L_x)$$_2$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=projection-based_wf-in-dft_embedding&rev=1720773475&do=diff Projection-based WF-in-DFT embedding Embedding methods allow a system to be divided into two smaller subsystems, each of which can be treated using a different level of theory. For example, in wavefunction-in-DFT (WF-in-DFT) embedding, a WF-level (e.g. HF, MP2, CCSD(T), CASSCF, etc.) calculation is performed on one subsystem, while a DFT-level calculation is performed on the other subsystem. The interactions between the two subsystems are calculated at the DFT level. The primary advantage of WF… text/html 2025-09-10T06:37:32+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=properties_and_expectation_values&rev=1757486252&do=diff Properties and expectation values The property program The property program allows the evaluation of one-electron operators and expectation values. Normally, the operators are computed automatically when using the global GEXPEC directive (see section $\ne 0$$z$$m=0$$x$$y$$z$$1,2,3,\ldots$$r$$P$$S$$|P-S|/r(S)$$\vec\mu=(\mu_x, \mu_y, \mu_z)$$H_1=\vec d \cdot \vec \mu$$\vec d=(\textit{dx},\textit{dy},\textit{dz})$$\vec F= -\vec d$$$|\vec F|^{-1}\vec F \cdot \vec \mu = |2\vec d|^{-1}(E(\vec d)-E(… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=qm_mm_interfaces&rev=1720773475&do=diff QM/MM interfaces The Molpro program package can be used in combination with other software to perform hybrid Quantum Mechanics/Molecular Mechanics (QM/MM) calculations. Through the use of point charges, electrostatic embedding can be used for both energy and gradient runs. In particular, lattices of point charges can be included in an external file, gradients with respect to charge positions can be computed, as described in section $NVE$$NVT$$NPT$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=quasi-diabatization&rev=1720773475&do=diff Quasi-diabatization The DDR procedure can also be used to generate quasi-diabatic states and energies for MRCI wavefucntions (CASSCF case can be treated as special case using the NOEXC directive in the MRCI). The quasi-diabatic states have the property that they change as little as possible relative to a reference geometry; with other words, the overlap between the states at the current geometry with those at a reference geometry is maximized by performing a unitary transformation among the giv… text/html 2025-10-14T08:54:13+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=quickstart&rev=1760432053&do=diff Quickstart The intention of this quickstart section is to get you started quickly. Most input is explained using simple examples. Default values are used as much as possible to make the inputs very simple. Naturally, this is by no means an exhaustive description of Molpro. A more systematic and complete explanation of all features of Molpro can be found in the later sections of the manual. We strongly recommend that you read the introductory chapters of the reference manual once you have gained… text/html 2025-10-25T07:22:46+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=recent_changes&rev=1761376966&do=diff Recent changes Several well parallelized new methods have been implemented in Molpro. A review of recent developments in Molpro can be found in J. Chem. Phys. 152, 144107 (2020). We recommend always to use the most recent version, since developments are ongoing and problems reported by users are always fixed as quickly as possible. In particular, before reporting bugs, please check if these still occur in the latest version.$10^{-8}$$10^{-9}$$10^{-6}$$10^{-7}$$_x$$_y$$_z$$C_6$$C_8$$C_{10}$$_{\… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=references&rev=1720773475&do=diff References All publications resulting from use of this program must acknowledge the following three references. H.-J. Werner, P. J. Knowles, G. Knizia, F. R. Manby and M. Schütz, WIREs Comput Mol Sci 2, 242–253 (2012), doi: 10.1002/wcms.82 Hans-Joachim Werner, Peter J. Knowles, Frederick R. Manby, Joshua A. Black, Klaus Doll, Andreas Heßelmann, Daniel Kats, Andreas Köhn, Tatiana Korona, David A. Kreplin, Qianli Ma, Thomas F. Miller, III, Alexander Mitrushchenkov, Kirk A. Peterson, Iakov Poly… text/html 2025-05-27T08:28:11+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=region&rev=1748334491&do=diff Region The REGION program allows a correlated method to be applied to a target region within a molecule, where it is restricted to a subset of spatially localised orbitals, and the rest of the valence electrons left uncorrelated and only treated at the mean-field level.$1.0\times10^{-8}$$$E = E_{low}(A+B) - E^{reg}_{low}(A) + E^{reg}_{high}(A).$$$A$$B$$E^{reg}_{low}(A)$$E^{reg}_{high}(A)$$1.0\times10^{-8}$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=relativistic_corrections&rev=1720773475&do=diff Relativistic corrections There are three ways in Molpro to take into account scalar relativistic effects: * Use the Douglas-Kroll-Hess or eXact-2-Component (X2C) relativistic one-electron integrals. * Compute a perturbational correction using the Cowan-Griffin operator (see section $n$$n=2,\dots,99$$m$$m=1,\dots,5$$n$$m$ text/html 2025-06-03T07:32:59+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=running_molpro&rev=1748935979&do=diff Running Molpro On Unix systems, Molpro is accessed using the molpro unix command. The syntax is molpro options datafile Molpro’s execution is controlled by user-prepared data; if datafile is not given on the command line, the data is read from standard input, and program results go to standard output. Otherwise, data is taken from $=$$\dots$ text/html 2025-02-07T12:55:01+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=running_molpro_on_parallel_computers&rev=1738932901&do=diff Running Molpro on parallel computers Molpro will run on distributed-memory multiprocessor systems, including workstation clusters, under the control of the Global Arrays parallel toolkit or the MPI-2 library. There are also some parts of the code that can take advantage of shared memory parallelism through the $M$$(n \cdot m+G)/N$$n$$m$$G$$N$$8\cdot[n\cdot(m+0.3)+G]/N$$n,m,G$$M$$m=M\cdot N/(2\cdot n)$$G=N\cdot M/2$$m$$G$$m$$G$$M$$m$$G$$m$$G$$M=2G$$32$$nprocs\_per\_server=8$$8$$4$$nprocs\_per\_s… text/html 2025-03-04T09:08:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=smiles&rev=1741079335&do=diff SMILES (Molecular integrals with Slater functions) SMILES is a package for molecular integrals with Slater functions implemented by J. Fernandez Rico, R. Lopez, G. Ramirez, I. Ema, D. Zorrilla and K.Ishida. It combines several techniques for the evaluation of the different types of integrals, a summary of which can be found in J. Fernandez Rico, R. Lopez, G. Ramirez, I. Ema, $(AB|AC)$$(AB|CD)$$(n,l)$$(AB|AC)$$(AB|CB)$$_2$$_2$ text/html 2025-07-23T06:54:28+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=spin-orbit-coupling&rev=1753253668&do=diff Spin-orbit-coupling Introduction Spin-orbit matrix elements and eigenstates can be computed using either the Breit-Pauli (BP) operator or spin-orbit pseudopotentials (ECPs). The state-interacting method is employed, which means that the spin-orbit eigenstates are obtained by diagonalizing $\hat H_{el} + \hat H_{SO}$$\hat H_{el}$$^{-1}$$10^{-7}$$2 \times M_S$$2 \times M_S$${\tt LSX}$${\tt LSY}$${\tt LSZ}$${\tt ECPLSX}$${\tt ECPLSY}$${\tt ECPLSZ}$$M_S$$\Delta M_S = \pm 1$$\Delta M_S=0$$2M_S$$x$$… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=split_coulomb_operator_treatment_attenuate&rev=1720773475&do=diff Split Coulomb operator treatment (ATTENUATE) This directive activates the method described in G. Hetzer, M. Schütz, H. Stoll, and H.-J. Werner, Low-order scaling local electron correlation methods II: Splitting the Coulomb operator in linear scaling local MP2$\ldots$$\omega$$p$$p$$r$$\phi$$r$$\omega$$r$$\phi$$\gamma=1.0$$x$$y$$z$$2^{p+1}$$p$$2^{p+1}$$2^p$$2^{p-1}$ text/html 2024-10-21T20:45:20+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=symmetry-adapted_intermolecular_perturbation_theory&rev=1729543520&do=diff Symmetry-adapted intermolecular perturbation theory Introduction The SAPT (symmetry-adapted intermolecular perturbation theory) program calculates the total interaction energy between closed-shell molecules as a sum of individual first and second order interaction terms, namely electrostatic $E_{\text{pol}}^{(1)}$$E_{\text{ind}}^{(2)}$$E_{\text{disp}}^{(2)}$$E_{\text{exch}}^{(1)}$$E_{\text{exch-ind}}^{(2)}$$E_{\text{exch-disp}}^{(2)}$$[1]$$[2]$$[3]$$[4]$$[5]$$[6]$$[7]$$[8]$$[9]$$[10]$$[11]$$[1… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=tables_and_plotting&rev=1720773475&do=diff Tables and plotting Tables Variables can be printed in Table form using the command TABLE,var1,var2,… The values of each variable are printed in one column, so all variables used must be defined for the same range, and corresponding elements should belong together. For example, if in a calculation one has stored $n$$n$$\dots$$\dots$$n$$m$$m$$(x,y)$$n$$m$$_{\rm e}$$_0$$_{\rm e}$$_0$ text/html 2025-11-05T11:23:35+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=table_of_contents&rev=1762341815&do=diff Table of Contents * Introduction to Molpro * Molpro on the www * References * Installation guide * Recent changes * Quickstart * How to read this manual * Running Molpro * Running Molpro on parallel computers * gmolpro graphical user interface * Definition of Molpro input language * General program structure * Introductory examples * General hints - frequently asked questions * Program control * File handling * Variables * Tables and plotting * Molecular g… text/html 2025-08-04T20:53:11+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_closed-shell_density_fitting_cc2_program_for_ground_and_excited_states&rev=1754340791&do=diff The closed-shell density fitting CC2 program for ground and excited states The CC2 method is an approximate CCSD (coupled-cluster singles and doubles) method which retains the same singles equation as the CCSD model, but in which the doubles amplitude equation is approximated to first order in the $T_2$$N^4$$N^5$$5$$1$$3$$4$$4$$6$$=1$$=\langle record\rangle.\langle file \rangle$$\langle record\rangle.\langle file \rangle$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_closed_shell_ccsd_program&rev=1720773475&do=diff The closed shell CCSD program Bibliography: C. Hampel, K. Peterson, and H.-J. Werner, Chem. Phys. Lett. 190, 1 (1992) All publications resulting from use of this program must acknowledge the above. The CCSD program is called by the CISD, CCSD, BCCD, or QCI directives. CID or CCD can be done as special cases using the $T_1$$D_1$$\Delta T$ text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_cosmo_model&rev=1720773475&do=diff The COSMO model The Conductor-like Screening Model (COSMO) (A. Klamt and G. Schüürmann, J. Chem. Soc. Perkin Trans. II 799-805 (1993)) is currently available for HF (RHF,UHF) and DFT (RKS,UKS) energy calculations and the corresponding gradients. $value = 10 \times 3^k \times 4^l +2$$values = 10 \times 3^k \times 4^l +2$$\epsilon=\infty$$\bf A$$<$$\times$$r^{out}_i=r_i+ROUTF \times RSOLV$$\times$$\epsilon$$${\bf q^{*}} = -{\bf A^{-1}} \Phi$$$\Phi$$\bf A$$f(\epsilon)$$${\bf q} = f(\epsilon) {\bf… text/html 2025-01-09T09:54:42+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_density_functional_program&rev=1736416482&do=diff The density functional program Density-functional theory calculations may be performed using one of the following commands: * DFT calculate functional of a previously computed density. * RKS or RKS-SCF calls the spin-restricted Kohn-Sham program. $\dots$$\dots$$\ldots$$a_x$$a_c$$a_x E_x^{\text{HF}} + (1-a_x) E_x^{\text{DFT}}[\rho] + (1-a_c) E_c^{\text{DFT}}[\rho]$$a_c E_c^{\text{MP2}}$$a_c$$a_c=a_x^2$$a_x$$a_c$$a_x E_x^{\text{HF}} + (1-a_x) E_x^{\text{DFT}}[\rho] + E_c^{\text{DFT}}[\rho] -… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_full_ci_program&rev=1720773475&do=diff The full CI program This module is the determinant full CI program, as described in P.J. Knowles and N.C. Handy, Chem. Phys. Lett. 111, 315 (1984), P.J. Knowles and N.C. Handy, Comp. Phys. Commun. 54 (1989) 75. Published work resulting from the use of this program should cite these references.$n_1,n_2,\ldots,n_8$$n_i$$i$$n_1,n_2,\ldots,n_8$$n_i$$i$$=2S$$10^{-5}$ text/html 2025-07-22T07:08:06+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_mcscf_program_multi&rev=1753168086&do=diff The MCSCF program MULTI MULTI is a general MCSCF/CASSCF program written by P. J. Knowles and H.-J. Werner (1984) D. Kreplin, P. J. Knowles, and H.-J. Werner (2019) Bibliography: Second-order MCSCF: H.-J. Werner and P. J. Knowles, J. Chem. Phys. 82, 5053 (1985).$N$$\Lambda$$\Sigma$$\Pi$$\Delta$$n_1,n_2,...,n_8$$n_i$$i$$n_1,n_2,\ldots,$$n_i$$i$$n_i$$1s$$1s2s2p$$n_1,n_2,\ldots,n_8$$n_i$$i$$=2S$$w(1),w(2),\ldots, w($$)$$w(i)$$i$$$w=1/\cosh(dynfac*\Delta E)^2$$$\Delta E$$\Delta E$$\ldots$$_1$$… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_mrcc_program_of_m._kallay_mrcc&rev=1720773475&do=diff The MRCC program of M. Kallay (MRCC) An interface exists to use the MRCC program of M. Kallay and J. Gauss within Molpro. The license and source code of the MRCC program must be obtained from Mihaly Kallay http://www.mrcc.hu/. Currently, only single reference methods with text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_mrci_program&rev=1720773475&do=diff The MRCI program Multiconfiguration reference internally contracted configuration interaction Bibliography: H.-J. Werner and P.J. Knowles, J. Chem. Phys. 89, 5803 (1988). P.J. Knowles and H.-J. Werner, Chem. Phys. Lett. 145, 514 (1988). For excited state calculations: P. J. Knowles and H.-J. Werner, Theor. Chim. Acta $n_1,n_2,\ldots,n_8$$n_i$$i$$n_1,n_2,\ldots,n_8$$n_i$$i$$n_1,n_2,\ldots,n_8$$n_i$$i$$=2S$$C_s$$\Pi$$A'$$A''$$A'$$C_{2v}$$\ldots$$_1$$_2$$\ldots$$_n$$n_1,n_2,n_3,n_4,\ldots$$n_… text/html 2024-11-05T08:47:21+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_nevpt2_program&rev=1730796441&do=diff The NEVPT2 program Reference literature: C. Angeli, R. Cimiraglia, S. Evangelisti, T. Leininger and J. P. Malrieu, J. Chem. Phys., 114,10252, (2001) C. Angeli, R. Cimiraglia and J. P. Malrieu, J. Chem. Phys. 117, 9138, (2002) C. Angeli, M. Pastore and R. Cimiraglia, $S^2$$S_z$$^1A_2$$n \to \pi^*$ text/html 2025-09-25T13:22:01+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_scf_program&rev=1758806521&do=diff The SCF program The Hartree-Fock self-consistent field program is invoked by one of the following commands: * HF or RHF calls the spin-restricted Hartree-Fock program * UHF or UHF-SCF,options calls the spin-unrestricted Hartree-Fock program In contrast to older versions of $\mu$$10^{-6})$$10^{-8}$$> 1$$10^{-accu}$$-0.3$$\alpha$$\beta$$=0$$=10$$\ge 0$$\pm$$>0$$spin=2*S$$n_1,n_2,\ldots,n_8$$n_i$$i$$n_1,n_2,\ldots,n_8$$orb_1.sym_1,orb_2.sym_2,\ldots,orb_n.sym_n$$orb_i.sym$$\alpha$$\beta$$h$$… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_tdhf_and_tdks_programs&rev=1720773475&do=diff The TDHF and TDKS programs Real-time electronic dynamics using time-dependent Hartree-Fock and time-dependent Kohn-Sham theories can be performed using the commands TDHF and TDKS respectively, which have to be preceded by a HF and KS command. Unrestriced versions are available through $\mathbf{128}$$>2$$>2$$e_q$$q$$e_q$$q$$\alpha$$e_q$$q$$\omega$$e_q$$\alpha$$e_q$$q$$\omega$$e_q$$q$$\omega$$\sin^2$$\alpha$$\alpha$$\beta$$ng>2$$ng^3$ text/html 2025-07-18T10:44:49+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=the_vb_program_casvb&rev=1752835489&do=diff The VB program CASVB CASVB is a general program for valence bond calculations written by T. Thorsteinsson and D. L. Cooper (1996–2005). This program can be used in two basic modes: * variational optimization of quite general types of nonorthogonal MCSCF or so-called modern valence bond wavefunctions;$mcore$$mact$$Nact$$n_1,n_2,n_3,n_4,\ldots$$n_i$$i$$Nact$$\phi_1\phi_2\cdots\phi_{Nact}$$i$$mact$$NVB$$i_1$$i_{mact}$$\phi_j'={\rm sign}(i_j)\phi_{{\rm abs}(i_j)}$$${\rm max}\left(\frac{\langl… text/html 2024-07-12T08:37:55+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=time-dependent_density_functional_theory&rev=1720773475&do=diff Time-dependent density functional theory Excitation energies and linear response properties can be calculated utilising the time-dependent density functional theory (TDDFT) method. The program should normally be called after a Kohn-Sham or Hartree-Fock calculation because it looks for the most recent orbital dump record to read in the MO coefficients and orbital energies. Further settings like the functional type and quadrature grid are then adopted from the previous ground-state calculation, y… text/html 2025-04-28T11:29:12+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=variables&rev=1745839752&do=diff Variables Data may be stored in variables. A variable can be of type string, real or logical, depending on the type of the expression in its definition. Any sequence of characters which is not recognized as expression or variable is treated as string. In this section, we will discuss only $2\cdot M\_S$$\times$$2*M_S$$\nabla^4$$L^2$$(i-1)*(i-2)/2+j$$i \gt j \ge 1$$i$$L_z^2$ text/html 2024-11-14T14:22:22+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=vibrational_perturbation_theory_vpt2&rev=1731594142&do=diff Vibrational perturbation theory (VPT2) VPT2,options The VPT2 program is based on force constants, which are retrieved from the polynomial coefficients as generated by the POLY program. Therefore, each VPT2 calculation requests a call of the POLY program prior to the $2\omega_i - \omega_k$$\omega_i + \omega_j - \omega_k$ text/html 2025-05-22T10:35:17+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=vibrational_scf_programs&rev=1747910117&do=diff The VSCF programs (VSCF) VSCF,options [vscf] The VSCF program is exclusively based on the Watson Hamiltonian \begin{align} \hat{H} = \frac{1}{2} \sum_{\alpha\beta} ( \hat{J}_\alpha - \hat{\pi}_\alpha) \mu_{\alpha\beta} (\hat{J}_\beta - \hat{\pi}_\beta) -\frac{1}{8}\sum_\alpha \mu_{\alpha\alpha} -\frac{1}{2}\sum_i \frac{\partial^2}{\partial q_i^2} + V(q_1,\dots,q_{3N-6}) \label{eq:1} \end{align} in which the potential energy surfaces, $V(q_1,\dots,q_{3N-6})$, are provided by the XSURF module. … text/html 2025-05-22T14:03:41+00:00 Anonymous (anonymous@undisclosed.example.com) https://www.molpro.net/manual/doku.php?id=vibration_correlation_programs&rev=1747922621&do=diff Vibration correlation programs The VCI program (VCI) VCI,options VCI calculations account for vibration correlation effects and use potential energy surfaces as generated from the XSURF program and a basis of VSCF modals or harmonic oscillator functions. For each vibrational state an individual $(1^42^43^4)$$(1^42^3)$$(1^32^33^1)$$(1^32^23^2), ...$$l$$0\rightarrow 1$$0\rightarrow 2$$0\rightarrow 3$$n$$n$$n$$\alpha$$\left < VSCF \left | q_i^r \right | VSCF \right >$$\times$$5\cdot 10^{-10}$$^{…