Understanding the Role of Dispersion in Frustrated Lewis Pairs and Classical Lewis Adducts: A Domain-Based Local Pair Natural Orbital Coupled Cluster Study.

The interaction of Lewis acids and bases in both classical Lewis adducts and frustrated Lewis pairs (FLPs) is investigated to elucidate the role that London dispersion plays in different situations. The analysis comprises 14 different adducts between tris(pentafluorophenyl)borane and a series of phosphines, carbenes, and amines with various substituents, differing in both steric and electronic properties. The domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD(T)) method is used in conjunction with the recently introduced local energy decomposition (LED) analysis to obtain state-of-the-art dissociation energies and, at the same time, a clear-cut definition of the London dispersion component of the interaction, with the ultimate goal of aiding in the development of designing principles for acid/base pairs with well-defined bonding features and reactivity. In agreement with previous DFT investigations, it is found that the London dispersion dominates the interaction energy in FLPs, and is also remarkably strong in Lewis adducts. In these latter systems, its magnitude can be easily modulated by modifying the polarizability of the substituents on the basic center, which is consistent with the recently introduced concept of dispersion energy donors. By counteracting the destabilizing energy contribution associated with the deformation of the monomers, the London dispersion drives the stability of many Lewis adducts.

[1]  Frank Neese,et al.  Decomposition of Intermolecular Interaction Energies within the Local Pair Natural Orbital Coupled Cluster Framework. , 2016, Journal of chemical theory and computation.

[2]  C. Bannwarth,et al.  Dispersion-Corrected Mean-Field Electronic Structure Methods. , 2016, Chemical reviews.

[3]  L. Rincón,et al.  On the thermodynamic stability of the intermolecular association between Lewis acids and Lewis bases: a DFT study , 2016, Theoretical Chemistry Accounts.

[4]  C. Adamo,et al.  Investigating the role of the π-bridge characteristics in donor–π-spacer–acceptor type dyes for solar cell application: a theoretical study , 2016, Theoretical Chemistry Accounts.

[5]  Frank Neese,et al.  Sparse maps--A systematic infrastructure for reduced-scaling electronic structure methods. II. Linear scaling domain based pair natural orbital coupled cluster theory. , 2016, The Journal of chemical physics.

[6]  J. Wagner,et al.  London’sche Dispersionswechselwirkungen in der Molekülchemie – eine Neubetrachtung sterischer Effekte , 2015 .

[7]  P. Schreiner,et al.  London dispersion in molecular chemistry--reconsidering steric effects. , 2015, Angewandte Chemie.

[8]  Frank Neese,et al.  Sparse maps—A systematic infrastructure for reduced-scaling electronic structure methods. I. An efficient and simple linear scaling local MP2 method that uses an intermediate basis of pair natural orbitals. , 2015, The Journal of chemical physics.

[9]  G. Erker,et al.  Frustrated Lewis pair chemistry: development and perspectives. , 2015, Angewandte Chemie.

[10]  G. Erker,et al.  Chemie frustrierter Lewis‐Paare: Entwicklung und Perspektiven , 2015 .

[11]  P. Geerlings,et al.  Conceptual quantum chemical analysis of bonding and noncovalent interactions in the formation of frustrated Lewis pairs. , 2015, Chemistry.

[12]  Manoj K. Kesharwani,et al.  Exploring the Accuracy Limits of Local Pair Natural Orbital Coupled-Cluster Theory. , 2015, Journal of chemical theory and computation.

[13]  C. Bannwarth,et al.  The Association of Two “Frustrated” Lewis Pairs by State-of-the-Art Quantum Chemical Methods , 2015 .

[14]  C. Bannwarth,et al.  The Thermochemistry of London Dispersion-Driven Transition Metal Reactions: Getting the ‘Right Answer for the Right Reason’ , 2014, ChemistryOpen.

[15]  A. Macchioni,et al.  Probing the association of frustrated phosphine-borane Lewis pairs in solution by NMR spectroscopy. , 2014, Journal of the American Chemical Society.

[16]  G. Röschenthaler,et al.  On the mechanism of hydrogen activation by frustrated Lewis pairs. , 2013, Chemistry.

[17]  Frank Neese,et al.  Natural triple excitations in local coupled cluster calculations with pair natural orbitals. , 2013, The Journal of chemical physics.

[18]  Edward F. Valeev,et al.  What is the most efficient way to reach the canonical MP2 basis set limit? , 2013 .

[19]  I. Pápai,et al.  Reactivity models of hydrogen activation by frustrated Lewis pairs: synergistic electron transfers or polarization by electric field? , 2013, Journal of the American Chemical Society.

[20]  D. Camaioni,et al.  A thermodynamic and kinetic study of the heterolytic activation of hydrogen by frustrated borane-amine Lewis pairs. , 2013, Dalton transactions.

[21]  Frank Neese,et al.  An efficient and near linear scaling pair natural orbital based local coupled cluster method. , 2013, The Journal of chemical physics.

[22]  Jeng-Da Chai,et al.  Long-Range Corrected Hybrid Density Functionals with Improved Dispersion Corrections. , 2012, Journal of chemical theory and computation.

[23]  S. Grimme.  Supramolecular binding thermodynamics by dispersion-corrected density functional theory. , 2012, Chemistry.

[24]  I. Pápai,et al.  Association of frustrated phosphine-borane pairs in toluene: molecular dynamics simulations. , 2012, Dalton transactions.

[25]  F. Neese,et al.  Efficient and accurate local single reference correlation methods for high-spin open-shell molecules using pair natural orbitals. , 2011, The Journal of chemical physics.

[26]  Dimitrios G Liakos,et al.  Weak Molecular Interactions Studied with Parallel Implementations of the Local Pair Natural Orbital Coupled Pair and Coupled Cluster Methods. , 2011, Journal of chemical theory and computation.

[27]  Frank Neese,et al.  Revisiting the Atomic Natural Orbital Approach for Basis Sets: Robust Systematic Basis Sets for Explicitly Correlated and Conventional Correlated ab initio Methods? , 2011, Journal of chemical theory and computation.

[28]  S. Grimme,et al.  Electric field induced activation of H2--can DFT do the job? , 2010, Chemical communications.

[29]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[30]  S. Grimme,et al.  Neue Einblicke in den Mechanismus der Diwasserstoff‐Aktivierung durch frustrierte Lewis‐Paare , 2010 .

[31]  S. Grimme,et al.  The mechanism of dihydrogen activation by frustrated Lewis pairs revisited. , 2010, Angewandte Chemie.

[32]  G. Erker,et al.  Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr , 2010 .

[33]  Douglas W Stephan,et al.  Frustrated Lewis pairs: metal-free hydrogen activation and more. , 2010, Angewandte Chemie.

[34]  Y. M. Rhee,et al.  Dispersion-oriented soft interaction in a frustrated Lewis pair and the entropic encouragement effect in its formation. , 2009, Chemistry.

[35]  S. Geier,et al.  From classical adducts to frustrated Lewis pairs: steric effects in the interactions of pyridines and B(C6F5)3. , 2009, Inorganic chemistry.

[36]  Dimitrios G Liakos,et al.  Efficient and accurate approximations to the local coupled cluster singles doubles method using a truncated pair natural orbital basis. , 2009, The Journal of chemical physics.

[37]  Tibor András Rokob,et al.  Rationalizing the reactivity of frustrated Lewis pairs: thermodynamics of H(2) activation and the role of acid-base properties. , 2009, Journal of the American Chemical Society.

[38]  Wilfried Meyer,et al.  Ionization energies of water from PNO‐CI calculations , 2009 .

[39]  F. Neese,et al.  Efficient and accurate local approximations to coupled-electron pair approaches: An attempt to revive the pair natural orbital method. , 2009, The Journal of chemical physics.

[40]  Frank Neese,et al.  Accurate theoretical chemistry with coupled pair models. , 2009, Accounts of chemical research.

[41]  Douglas W. Stephan,et al.  Lutidine/B(C6F5)3: at the boundary of classical and frustrated Lewis pair reactivity. , 2009, Journal of the American Chemical Society.

[42]  Cristian G. Hrib,et al.  Heterolytic dihydrogen activation by a frustrated carbene-borane Lewis pair. , 2008, Angewandte Chemie.

[43]  Tibor András Rokob,et al.  Turning frustration into bond activation: a theoretical mechanistic study on heterolytic hydrogen splitting by frustrated Lewis pairs. , 2008, Angewandte Chemie.

[44]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[45]  Gregory C. Welch,et al.  Reactivity of "frustrated Lewis pairs": three-component reactions of phosphines, a borane, and olefins. , 2007, Angewandte Chemie.

[46]  R. Bartlett,et al.  Coupled-cluster theory in quantum chemistry , 2007 .

[47]  Gregory C. Welch,et al.  Facile heterolytic cleavage of dihydrogen by phosphines and boranes. , 2007, Journal of the American Chemical Society.

[48]  Jason D. Masuda,et al.  Reversible, Metal-Free Hydrogen Activation , 2006, Science.

[49]  A. Becke,et al.  A density-functional model of the dispersion interaction. , 2005, The Journal of chemical physics.

[50]  F. Weigend,et al.  Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy. , 2005, Physical chemistry chemical physics : PCCP.

[51]  Trygve Helgaker,et al.  Basis-set convergence in correlated calculations on Ne, N2, and H2O , 1998 .

[52]  Trygve Helgaker,et al.  Basis-set convergence of correlated calculations on water , 1997 .

[53]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[54]  Marco Häser,et al.  Auxiliary basis sets to approximate Coulomb potentials , 1995 .

[55]  José M. Pérez-Jordá,et al.  A density-functional study of van der Waals forces: rare gas diatomics. , 1995 .

[56]  Peter Pulay,et al.  CAN (SEMI) LOCAL DENSITY FUNCTIONAL THEORY ACCOUNT FOR THE LONDON DISPERSION FORCES , 1994 .

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

[58]  J. Vrbancich,et al.  Polarizability anisotropy, magnetic anisotropy, and quadrupole moment of cyclohexane , 1989 .

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

[60]  N. Hush,et al.  The coupled-pair approximation in a basis of independent-pair natural orbitals , 1976 .

[61]  R. Ahlrichs,et al.  Direct determination of pair natural orbitals , 1975 .

[62]  H. Lischka,et al.  PNO–CI (pair natural orbital configuration interaction) and CEPA–PNO (coupled electron pair approximation with pair natural orbitals) calculations of molecular systems. II. The molecules BeH2, BH, BH3, CH4, CH−3, NH3 (planar and pyramidal), H2O, OH+3, HF and the Ne atom , 1975 .

[63]  Wilfried Meyer,et al.  PNO–CI Studies of electron correlation effects. I. Configuration expansion by means of nonorthogonal orbitals, and application to the ground state and ionized states of methane , 1973 .

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

[65]  M. Krauss,et al.  Pseudonatural Orbitals as a Basis for the Superposition of Configurations. I. He2 , 1966 .

[66]  M. Krauss,et al.  Configuration‐Interaction Calculation of H3 and H2 , 1965 .

[67]  S. F. Boys.  Construction of Some Molecular Orbitals to Be Approximately Invariant for Changes from One Molecule to Another , 1960 .

[68]  Frank Neese,et al.  The ORCA program system , 2012 .

[69]  I. Pápai,et al.  Mechanism of hydrogen activation by frustrated Lewis pairs: A molecular orbital approach† , 2009 .