Polarizable density embedding: a new QM/QM/MM-based computational strategy.

We present a new QM/QM/MM-based model for calculating molecular properties and excited states of solute-solvent systems. We denote this new approach the polarizable density embedding (PDE) model, and it represents an extension of our previously developed polarizable embedding (PE) strategy. The PDE model is a focused computational approach in which a core region of the system studied is represented by a quantum-chemical method, whereas the environment is divided into two other regions: an inner and an outer region. Molecules belonging to the inner region are described by their exact densities, whereas molecules in the outer region are treated using a multipole expansion. In addition, all molecules in the environment are assigned distributed polarizabilities in order to account for induction effects. The joint effects of the inner and outer regions on the quantum-mechanical core part of the system is formulated using an embedding potential. The PDE model is illustrated for a set of dimers (interaction energy calculations) as well as for the calculation of electronic excitation energies, showing promising results.

[1]  Benedetta Mennucci,et al.  A TDDFT/MMPol/PCM model for the simulation of exciton-coupled circular dichroism spectra. , 2014, Physical chemistry chemical physics : PCCP.

[2]  Walter Thiel,et al.  Toward QM/MM Simulation of Enzymatic Reactions with the Drude Oscillator Polarizable Force Field. , 2014, Journal of chemical theory and computation.

[3]  Benedetta Mennucci,et al.  Geometry Optimization in Polarizable QM/MM Models: The Induced Dipole Formulation. , 2014, Journal of chemical theory and computation.

[4]  Jógvan Magnus Haugaard Olsen,et al.  Nuclear Magnetic Shielding Constants from Quantum Mechanical/Molecular Mechanical Calculations Using Polarizable Embedding: Role of the Embedding Potential. , 2014, Journal of Chemical Theory and Computation.

[5]  Jacob Kongsted,et al.  Damped Response Theory in Combination with Polarizable Environments: The Polarizable Embedding Complex Polarization Propagator Method. , 2014, Journal of chemical theory and computation.

[6]  Luca Frediani,et al.  The Dalton quantum chemistry program system , 2013, Wiley interdisciplinary reviews. Computational molecular science.

[7]  Jacob Kongsted,et al.  The multi-configuration self-consistent field method within a polarizable embedded framework. , 2013, The Journal of chemical physics.

[8]  Johannes Neugebauer,et al.  State-Specific Embedding Potentials for Excitation-Energy Calculations. , 2013, Journal of chemical theory and computation.

[9]  Sydney H. Kaufman,et al.  On the photoabsorption by permanganate ions in vacuo and the role of a single water molecule. New experimental benchmarks for electronic structure theory. , 2013, Chemphyschem : a European journal of chemical physics and physical chemistry.

[10]  Kurt V. Mikkelsen,et al.  Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroaniline , 2013 .

[11]  Benedetta Mennucci,et al.  Toward a Unified Modeling of Environment and Bridge-Mediated Contributions to Electronic Energy Transfer: A Fully Polarizable QM/MM/PCM Approach. , 2012, Journal of chemical theory and computation.

[12]  Jógvan Magnus Haugaard Olsen,et al.  PERI-CC2: A Polarizable Embedded RI-CC2 Method. , 2012, Journal of chemical theory and computation.

[13]  D. Truhlar,et al.  Partial Atomic Charges and Screened Charge Models of the Electrostatic Potential. , 2012, Journal of chemical theory and computation.

[14]  Lucas Visscher,et al.  Molecular properties via a subsystem density functional theory formulation: a common framework for electronic embedding. , 2012, The Journal of chemical physics.

[15]  Trygve Helgaker,et al.  Recent advances in wave function-based methods of molecular-property calculations. , 2012, Chemical reviews.

[16]  Spencer R Pruitt,et al.  Fragmentation methods: a route to accurate calculations on large systems. , 2012, Chemical reviews.

[17]  Chris-Kriton Skylaris,et al.  Electrostatic embedding in large-scale first principles quantum mechanical calculations on biomolecules. , 2011, The Journal of chemical physics.

[18]  Jacob Kongsted,et al.  Scrutinizing the effects of polarization in QM/MM excited state calculations. , 2011, Physical chemistry chemical physics : PCCP.

[19]  Vincenzo Barone,et al.  Polarizable Force Fields and Polarizable Continuum Model: A Fluctuating Charges/PCM Approach. 1. Theory and Implementation. , 2011, Journal of chemical theory and computation.

[20]  T. Wesołowski,et al.  Importance of the intermolecular Pauli repulsion in embedding calculations for molecular properties: the case of excitation energies for a chromophore in hydrogen-bonded environments. , 2011, The journal of physical chemistry. A.

[21]  Jacob Kongsted,et al.  Solvation Effects on Electronic Transitions: Exploring the Performance of Advanced Solvent Potentials in Polarizable Embedding Calculations. , 2011, Journal of chemical theory and computation.

[22]  Kenneth Ruud,et al.  GEN1INT: A unified procedure for the evaluation of one‐electron integrals over Gaussian basis functions and their geometric derivatives , 2011 .

[23]  Jacob Kongsted,et al.  The polarizable embedding coupled cluster method. , 2011, Journal of Chemical Physics.

[24]  Luca Frediani,et al.  Excitation energies in solution: the fully polarizable QM/MM/PCM method. , 2011, The journal of physical chemistry. B.

[25]  Jacob Kongsted,et al.  Molecular Properties through Polarizable Embedding , 2011 .

[26]  Jacob Kongsted,et al.  Excited States in Solution through Polarizable Embedding , 2010 .

[27]  FRANCESCO AQUILANTE,et al.  MOLCAS 7: The Next Generation , 2010, J. Comput. Chem..

[28]  Johannes Neugebauer,et al.  On the calculation of general response properties in subsystem density functional theory. , 2009, The Journal of chemical physics.

[29]  Ivan S Ufimtsev,et al.  Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics. , 2009, Journal of chemical theory and computation.

[30]  K. Kistler,et al.  Solvatochromic shifts of uracil and cytosine using a combined multireference configuration interaction/molecular dynamics approach and the fragment molecular orbital method. , 2009, The journal of physical chemistry. A.

[31]  J. Kongsted,et al.  Electronic Energy Transfer in Condensed Phase Studied by a Polarizable QM/MM Model. , 2009, Journal of chemical theory and computation.

[32]  Walter Thiel,et al.  QM/MM methods for biomolecular systems. , 2009, Angewandte Chemie.

[33]  On the coupling of intermolecular polarization and repulsion through pseudo-potentials , 2009 .

[34]  Christoph R. Jacob,et al.  A flexible implementation of frozen‐density embedding for use in multilevel simulations , 2008, J. Comput. Chem..

[35]  S. Clima,et al.  Embedding Fragment ab Initio Model Potentials in CASSCF/CASPT2 Calculations of Doped Solids: Implementation and Applications. , 2008, Journal of chemical theory and computation.

[36]  Kazuo Kitaura,et al.  Extending the power of quantum chemistry to large systems with the fragment molecular orbital method. , 2007, The journal of physical chemistry. A.

[37]  Jacob Kongsted,et al.  Density functional self-consistent quantum mechanics/molecular mechanics theory for linear and nonlinear molecular properties: Applications to solvated water and formaldehyde. , 2007, The Journal of chemical physics.

[38]  D. Truhlar,et al.  QM/MM: what have we learned, where are we, and where do we go from here? , 2007 .

[39]  Combined multireference configuration interaction/ molecular dynamics approach for calculating solvatochromic shifts: application to the n(O) --> pi* electronic transition of formaldehyde. , 2006, The journal of physical chemistry. A.

[40]  Jean-Philip Piquemal,et al.  Quantum mechanics/molecular mechanics electrostatic embedding with continuous and discrete functions. , 2006, The journal of physical chemistry. B.

[41]  U. Ryde,et al.  Comparison of overlap-based models for approximating the exchange-repulsion energy. , 2006, The Journal of chemical physics.

[42]  T. Darden,et al.  Towards a force field based on density fitting. , 2006, The Journal of chemical physics.

[43]  Kirk A Peterson,et al.  Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc-Zn. , 2005, The Journal of chemical physics.

[44]  J. Tomasi,et al.  Quantum mechanical continuum solvation models. , 2005, Chemical reviews.

[45]  Roland Lindh,et al.  Local properties of quantum chemical systems: the LoProp approach. , 2004, The Journal of chemical physics.

[46]  N. Handy,et al.  A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) , 2004 .

[47]  Kurt V. Mikkelsen,et al.  Coupled Cluster/Molecular Mechanics Method: Implementation and Application to Liquid Water , 2003 .

[48]  J. G. Snijders,et al.  A discrete solvent reaction field model within density functional theory , 2003 .

[49]  Mark S. Gordon,et al.  The Effective Fragment Potential Method: A QM-Based MM Approach to Modeling Environmental Effects in Chemistry , 2001 .

[50]  K. Kitaura,et al.  Fragment molecular orbital method: an approximate computational method for large molecules , 1999 .

[51]  David,et al.  Gaussian basis sets for use in correlated molecular calculations . Ill . The atoms aluminum through argon , 1999 .

[52]  J. Thøgersen,et al.  Ultrafast Charge-Transfer Dynamics: Studies of p-Nitroaniline in Water and Dioxane , 1998 .

[53]  Jacopo Tomasi,et al.  A new integral equation formalism for the polarizable continuum model: Theoretical background and applications to isotropic and anisotropic dielectrics , 1997 .

[54]  Mark S. Gordon,et al.  An effective fragment method for modeling solvent effects in quantum mechanical calculations , 1996 .

[55]  Jacques Weber,et al.  Kohn-Sham equations with constrained electron density: an iterative evaluation of the ground-state electron density of interacting molecules , 1996 .

[56]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[57]  J. V. Lenthe,et al.  State of the Art in Counterpoise Theory , 1994 .

[58]  P. Surján,et al.  The reliability of the point charge model representing intermolecular effects in ab initio calculations , 1994 .

[59]  A. Warshel,et al.  Frozen density functional approach for ab initio calculations of solvated molecules , 1993 .

[60]  A. Becke.  Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[61]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[62]  Hermann Stoll,et al.  Results obtained with the correlation energy density functionals of becke and Lee, Yang and Parr , 1989 .

[63]  A. Stone.  The induction energy of an assembly of polarizable molecules , 1989 .

[64]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[65]  L. Seijo,et al.  The ab initio model potential representation of the crystalline environment. Theoretical study of the local distortion on NaCl:Cu+ , 1988 .

[66]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[67]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[68]  J. Olsen,et al.  Linear and nonlinear response functions for an exact state and for an MCSCF state , 1985 .

[69]  Timothy Clark,et al.  Efficient diffuse function‐augmented basis sets for anion calculations. III. The 3‐21+G basis set for first‐row elements, Li–F , 1983 .

[70]  W. L. Jorgensen,et al.  Comparison of simple potential functions for simulating liquid water , 1983 .

[71]  W. Hehre,et al.  Molecular orbital theory of the properties of inorganic and organometallic compounds. 3. STO‐3G basis sets for first‐ and second‐row transition metals , 1983 .

[72]  Mark S. Gordon,et al.  Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements , 1982 .

[73]  Jacopo Tomasi,et al.  Approximate evaluations of the electrostatic free energy and internal energy changes in solution processes , 1982 .

[74]  J. Tomasi,et al.  Electrostatic interaction of a solute with a continuum. A direct utilizaion of AB initio molecular potentials for the prevision of solvent effects , 1981 .

[75]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[76]  A. Millefiori,et al.  Electronic spectra and structure of nitroanilines , 1977 .

[77]  M. Levitt,et al.  Theoretical studies of enzymic reactions: dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme. , 1976, Journal of molecular biology.

[78]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[79]  J. Pople,et al.  Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules , 1972 .

[80]  S. Huzinaga,et al.  Theory of Separability of Many‐Electron Systems , 1971 .

[81]  S. F. Boys,et al.  The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors , 1970 .

[82]  J. Pople,et al.  Self‐Consistent Molecular‐Orbital Methods. I. Use of Gaussian Expansions of Slater‐Type Atomic Orbitals , 1969 .