Philippe Hiberty   

 
 


















Groupe de Chimie Théorique 
Bâtiment 490 
Université de Paris-Sud 
91405 ORSAY Cedex 
France 

Tel : 01 69 15 61 75 Fax : 01 69 15 44 47 
e-mail: philippe.hiberty@u-psud.fr 

Date de naissance: 31/05/48 
 

Thèmes de recherche : Théorie valence bond, chimie radicalaire, diagrammes de corrélation valence bond, instabilités de symétrie, états électroniques diabatiques, mésomérie en chimie organique. 

Objectifs : Etude de la réactivité chimique par les diagrammes de corrélation valence bond. Corrélations des énergies d'activation  aux propriétés des réactaifs. Méthodologie valence bond ab initio. 
Chimie radicalaire et en particulier étude des radicaux comportant des liaisons à un ou trois électrons, et recherche des méthodes ab initio  adaptées. 

Méthodes : ab initio avec corrélation électronique, ab initio valence bond. 

Environnement scientifique : Un groupe de chimie théorique et simulation comprenant 18 permanents ou doctorants théoriciens, et d'autres groupes comportant des expérimentateurs dans divers domaines de la chimie physique. 

Principaux résultats
(a) méthode BOVB, permettant de calculer des fonctions valence bond compactes et précises; 

(b) nombreux articles et mises au point sur le rôle de la délocalisation électronique et de l'aromaticité en chimie organique, ainsi que sur la théorie valence bond. 

(c) Mise au point de méthodes simples permettant l'études de radicaux présentant des liaisons à 3 électrons. Evaluation critique des méthodes de fonctionnelles de la densité pour de tels systèmes. Etude systématique des ruptures de symétrie et de pseudosymétries dans ces radicaux. Etude des effets de substituants sur les liaisons à 3 électrons. 

Formation : Thèse d'état soutenue en 1978, post-doc à l'université de Stanford et à Berkeley. 

Responsabilités : Animateur du groupe de Chimie Théorique au Laboratoire de Chimie Physique (-> Juin 2003) 

Distinctions: Grand Prix Philippe A. Guye de l'Académie des Sciences, juin 2002. 

                      Palmes académiques, février 2009.

Enseignement : Professeur à l'Ecole Polytechnique (1996-2007) Cours de Chimie Quantique

Vulgarisation:

        1) La Théorie de la Liaison de Valence, P. C. Hiberty et F. Volatron,

              Bulletin de l'Union des Physiciens 97, 7-28 (2003)

        2) Mésomérie: Le Benzène nouveau est arrivé, P. C. Hiberty,

              Plein Sud 56, 24 (2004)

        3) Mésomérie: du Benzène aux Etats de Transition Réactionnels, un Modèle Unifié de la
           Délocalisation Electronique, P. C. Hiberty,

              Techniques de l'Ingénieur RE 20, 1-6 (2004)


Livres :

            1) A Chemist's Guide to Valence Bond Theory, S. Shaik and P.C. Hiberty, Wiley, Hoboken, New Jersey, 2008.

            2) Introduction à la Chimie Quantique, P. Hiberty et Nguyen Trong Anh, Ellipses, Paris, 2008.


Publications :
 

152)    Charge-Shift Bonding Emerges as a Distinct Electron-Pair Bonding Family from Both Valence Bond and Molecular Orbital Theories, H. Zhang, D. Danovich, W. Wei, B. Braida, P. C. Hiberty et S. Shaik,

                J. Chem. Theory Comput. 10, 2410-2418 (2014)

151) A Valence Bond   Model for Electron-Rich Hypervalent Species. Application to SFn (n = 1, 2, 4), PF5 and ClF3, B. Braïda, T. Ribeyre et P. C. Hiberty,

                Chem. Eur. J. 20, 9643-9649 (2014)

150) On the Nature of Blue-Shifting Hydrogen Bonds, Y. Mo, C. Wang, L. Guan, B. Braïda, P.C. Hiberty, W. Wu,

                Chem. Eur. J. 27, 8444-8452 (2014)

149) The Nature of the 4th Bond in the Ground State of C2: The Quadruple Bond Conundrum, D. Danovich, P.C. Hiberty, W. Wu, H. Rzepa, S. Shaik,

                Chem. Eur. J. 20, 6220-6232 (2014)

148) The V state of ethylene: valence bond theory takes up the challenge, W. Wu, H.Zhang, B. Braida, S. Shaik, P.C. Hiberty

                Theoret. Chem. Acc. 133, 1441 (2014)

147) Multicenter Bonding in Ditetracyanoethylene Dianion: A Simple Aromatic Picture in Terms of Three-Electron Bonds, B. Braida, K. Hendrickx, D. Domin, J. P. Dinnocenzo, P. C. Hiberty

                J. Chem. Theory Comput. 9, 2276-2285 (2013)

146) The Essential Role of Charge-Shift Bonding in Hypervalent Prototype XeF2 B. Braida, P.C. Hiberty,

                Nature Chemistry 5, 417 (2013)


145) Bridging Cultures, P.C. Hiberty et S. Shaik, dans:

The Nature of the Chemical Bond Revisited, Vol. 1, S. Shaik et G. Frenking, Eds. Wiley, Hoboken, sous presse (2013).

144) The Valence Bond Perspective of the Chemical Bond, S. Shaik, D. Danovich, W. Wu et P.C. Hiberty, dans:

The Nature of the Chemical Bond Revisited, Vol. 1, S. Shaik et G. Frenking, Eds. Wiley, Hoboken, sous presse (2013).

143) The Valence Bond Workshop in Paris : the Phenix Rises from the Ashes, or Has a Love Story with MO-Based Theories Begun ? B. Braida, E. Derat, S. Humbel, P.C. Hiberty et S. Shaik,

                ChemPhysChem 13, 4029-4030 (2012).

142) A Valence Bond View of Isocyanides Electronic Structure, R. Ramozzi, N. Chéron, B. Braïda, P. C. Hiberty, P. Fleurat-Lessard

                New J. Chem. 36, 1137-1140 (2012)

141) In Defence of the Hybrid Atomic Orbitals P.C. Hiberty, F. Volatron, S. Shaik

                J. Chem. Ed. 89, 575-577 (2012).

140) Can Aromaticity Coexist with Diradical Character? An Ab Initio Valence Bond Study of S2N2 and Related 6-π-Electron Four-Membered Rings E2N2 and E42+ (E = S, Se, Te) B. Braida, A. Lo, P.C. Hiberty,

                 ChemPhysChem 13, 811-819 (2012)

139) Quadrupole Bonding in C2 and Analogous 8-Valence Electron Species  S. Shaik, D. Danovich, W. Wu, H. S. Rzepa, P.C. Hiberty,

                Nature Chemistry 4, 195-200 (2012)

138) Classical Valence Bond Approach by Modern Methods, W. Wu, P. Su, S. Shaik, et P.C. Hiberty,

                Chem. Rev. 111, 7557-7593 (2011).

137) Modern Ab Initio Valence Bond Methods, P. C. Hiberty et S. Shaik, dans :

Solving the Schrödinger Equation : Has Everything Been Tried ? P. Popelier, Ed. Imperial College Press, London, Chapitre 8, pp. 201-235 (2011).

136) The Nature of the Idealized Triple Bonds Between Principal Elements, and the s-Origins of Trans-Bent Geometries – A Valence Bond Study, E. Ploshnik, D. Danovich , P.C. Hiberty et S. Shaik, 

                J. Chem. Theor. Comput. 7, 955-968 (2011).

135) A Primer on Qualitative Valence Bond Theory — A Theory Coming of Age, S. Shaik et P. C. Hiberty,

                 WIREs Comput. Mol. Sci. 1, 18-29 (2011).

134) Cage-Breaking Cascade, P. C. Hiberty,

                   Nature Chemistry 3, 96 (2011).

133) Bonding Conundrums in the C2 Molecule : A Valence Bond Study, P. Su, J. Wu, W. Wu, S. Shaik et P.C. Hiberty,

                J. Chem. Theor. Comput. 7, 121 (2011).

132) How to Properly Compute the Resonance Energy Within the Ab Initio Valence Bond Theory. A Response to the ZHJVL Paper, Y. Mo, P.C. Hiberty, P.v.R. Schleyer,

                 Theor. Chem. Acc. 127, 27 (2010)

131)    A Clear Correlation Between the Diradical Character of 1,3-Dipoles and their Reactivity Towards Ethylene and Acetylene, B. Braïda, C. Walter, B. Engels et P.C. Hiberty,

                J. Amer. Chem. Soc. 132, 7631 (2010)

130)     Explicit Solvation Effects on the Conventional Resonance Model for Protonated Imine, Carbonyl and Thiocarbonyl Compounds, B. Braïda et P.C. Hiberty,

                Int. J. Quant. Chem. 110, 571 (2010).

129)     An Excursion from Normal to Inverted C-C Bonds Shows a Clear Demarcation between Covalent and Charge-Shift Bonds, S. Shaik, Z. Chen, W. Wu, A. Stanger, D. Danovich et P.C. Hiberty,

                    ChemPhysChem 10, 2658 (2009).

128)    New Concepts in Chemical Bonding: Charge-Shift Bonding and its Manifestations in Chemistry, S. Shaik, D. Danovich, W. Wu et P. C. Hiberty,

                 Nature Chemistry 1, 443 (2009).

127)    Valence Bond Perturbation Theory. A Valence Bond Method that Incorporates Perturbation Theory, Z Chen, J. Song, S. Shaik, P.C. Hiberty et W. Wu,

                  J. Phys. Chem. A 113, 11560 (2009).

126)    The Physical Origin of Saytzeff's Rule, B. Braida, V. Prana et P. C. Hiberty,

                 Angew. Chem. Int. Ed. 48, 5724 (2009).

125) The "Inverted" Bond in [1.1.1] Propellane is a Charge-Shift Bond, W. Wu, J. Gu, J. Song, S. Shaik et P. C. Hiberty,

                Angew. Chem. Int. Ed. 48, 1407 (2009).

124) Topology of Electron Charge Density for Chemical Bond from Valence Bond Theory: A Probe of Bonding Types, L. Zhang, F. Ying, W. Wu, P. C. Hiberty et S. Shaik,

               Chem. Eur. J. 15, 2979 (2009).

123) Application of the Valence Bond Mixing Configuration Diagrams to hypervalency in Trihalide Anions. A challenge to the Rundle-Pimentel Model, B. Braïda et P.C. Hiberty

             J. Phys. Chem. A 112, 13045 (2008).

122) A Valence Bond Study of the Low-lying States of the NF Molecule, P. Su, W. Wu, S. Shaik et P.C. Hiberty

            ChemPhysChem 9, 1442 (2008).

121) Testing the validity of the conventional resonance model for protonated carbonyl, imine and thiocarbonyl compounds. An ab initio valence bond study, B. Braïda, D. Bundhoo, B. Engels et P.C. Hiberty

             Org. Lett. 10, 1951 (2008).

120) Heterolytic Bond Dissociation in Water; Why so Easy for C4H9Cl But Not for C3H9SiCl? , P. Su, L. Song, W. Wu, S. Shaik et P.C. Hiberty,

             J. Phys. Chem. A 112, 2988 (2008)

119) The Menshutkin Reaction H3N + CH3Cl –> H3NCH3+ + Cl in the Gas Phase and in Aqueous Solution: A Valence Bond Study, P. Su, F. Ying, W. Wu, P.C. Hiberty, S. Shaik,

             ChemPhysChem 8, 2603 (2007)

118) A Valence Bond Study of the Dioxygen Molecule, P. Su, L. Song, W. Wu, P.C. Hiberty et S. Shaik,

             J. Comput. Chem. 28, 185 (2007)

117) A Survey of Recent Developments in Ab Initio Valence Bond Theory, P.C. Hiberty et S. Shaik,

             J. Comput. Chem. 28, 137 (2007)

116) A Valence Bond Approach of the Electronic Structures of Classical and Distonic Radical Cations, G. Bouchoux, F. Berruyer-Penaud, P.C. Hiberty et W. Wu,

             Chem. Eur. J. 13, 2912 (2007)

115) The Physical Origin of Large Covalent-ionic Energies in Some Two-electron bonds, P.C. Hiberty, L. Song, R. Ramozzi, W. Wu et S. Shaik,

             Faraday Discuss. 135, 261 (2007)

114) Ab Initio Conformational Study of the P6 Potential Surface. Evidence for a Low-lying One-electron-bonded Isomer, P.C. Hiberty et F. Volatron,                     

            Heteroatom Chemistry 18
, 129 (2007)

113) Identity SN2 Reactions X + CH3X –> XCH3 + X (X= F, Cl, Br, and I) in Vacuum and in Aqueous Solution: A Valence Bond Study, L. Song, W. Wu, P.C. Hiberty et S. Shaik,

             Chem. Eur. J. 12, 7458 (2006)

112) Barriers of Hydrogen Abstraction vs Halogen Exchange - An Experimental Manifestation of Charge-Shift Bonding, P.C. Hiberty, C. Megret, L. Song, W. Wu et S. Shaik,

            J. Amer. Chem. Soc. 128, 2836 (2006)

111) Charge-Shift Bonding - A Class of Electron-Pair Bonds Emerges from Valence Bond Theory and Supported by Electron Localization Function Approach, S. Shaik, D. Danovitch, B. Silvi, D. Lauvergnat et P.C. Hiberty, 

            Chem. Eur. J. 21, 6358 (2005).

110) Some Answers to Frequently Asked Questions About the Distortive Tendencies of ?-Electronic Systems, P. C. Hiberty et S. Shaik, 

            Theor. Chem. Acc. 114, 169 (2005)

109) The Valence Bond Diagram Approach - A Paradigm for Chemical Reactivity, S. Shaik et P. C. Hiberty , dans:

            Theory and Applications of Computational Chemistry: The first 40 years, C. E. Dykstra, K. S. Kim, G. Frenking et G. E. Scuseria, eds., Elsevier, Amsterdam, pp 635-668 (2005).

108) What Makes the Trifluoride Anion F3 so Special? A Breathing-Orbital Valence Bond Ab Initio Study, B. Braïda et P.C. Hiberty, 

             J. Amer. Chem. Soc. 126, 14890 (2004) 

107) Valence Bond Calculations of Hydrogen Transfer reaction: a General Predictive Pattern Derived from Theory, P. Su, L. Song, W. Wu, P.C. Hiberty et S. Shaik, 

            J. Amer. Chem. Soc. 126, 13539 (2004) 

106) Valence Bond Theory, its History, Fundamentals, and Applications. A Primer, S. Shaik et P.C. Hiberty, 

            Rev. Comp. Chem. 20, 1-100 (2004). 

105) The Distortive Tendencies of p-electronic Systems, their Relationship to Isoelectronic s-Bonded Analogs, and Observables: A Description Free of the Classical Paradoxes, P.C. Hiberty et S. Shaik, 

           Phys. Chem. Chem. Phys. 6, 224 (2004)

104)  Conversation on VB vs. MO Theory: A Never Ending Rivalry? R. Hoffmann, S. Shaik et P.C. Hiberty, 

           Acc. Chem. Res. 36, 750 (2003) 

103) An Accurate Barrier for the Hydrogen Exchange Reaction from Valence Bond Theory: Is this Theory Coming of Age? L. Song, W. Wu, P.C. Hiberty, D. Danovich et S. Shaik. 

            Chem. Eur. J. 9, 4540 (2003) 

102) A Simplified G2 Scheme for Determining Electron Affinities of Covalent Bonds. Application to the Disulfide Bond RS-SR' (R, R' : H, CH3, C2H5), B. Braïda et P.C. Hiberty, 

            J. Phys. Chem. A 107, 4741 (2003) 

101) Aromaticity and Antiaromaticity: What Role Do Ionic Configurations Play in Delocalization and Induction of Magnetic Properties? A. Shurki, P.C. Hiberty, F. Dijkstra et S. Shaik, 

            J. Phys. Org. Chem. 16,  731 (2003). 

100) Myth and Reality in the Attitude Toward Valence Bond (VB) : Are its "Failures" Real?S. Shaik et P.C. Hiberty, 

            Helvetica Chim. Acta 86, 1063 (2003) 

99) Valence Bond Modeling of Barriers in the Nonidentity Hydrogen Abstraction Reactions, X'o + H-X -> X'-H + Xo (X' * X = CH3, SiH3, GeH3, SnH3, PbH3), L. Song, W. Wu, K. Dong, P.C. Hiberty et S. Shaik, 

             J. Phys. Chem. A, , 106, 11361 (2002) 

98) BOVB - A Modern Valence Bond Method that Includes Dynamic Correlation, P.C. Hiberty et S. Shaik, 

            Theor. Chem. Acc. 108, 255-272 (2002) 

97) Stability, Metastabilty and Unstability of Three-Electron-Bonded Radical Anions. A Model ab initio Theoretical Study, B. Braïda, L. Thogersen et P.C. Hiberty 

            J. Amer. Chem. Soc. 124, 11781 (2002) 

96) BOVB - A Valence Bond Method Incorporating Static and Dynamic Correlation Effects, P. C. Hiberty and S. Shaik, dans: 

           Valence Bond Theory, D.L. Cooper and D.J. Klein, eds.,    Elsevier, Amsterdam, pp 187-225 (2002) 

95) Reply to Comment on " Identity Hydrogen Abstraction Reactions, X + H-X' -> X-H + X' (X=X' = CH3, SiH3, GeH3, SnH3, PbH3): A Valence Bond Modeling, S. Shaik, S.P. de Visser, W. Wu, L. Song et P.C. Hiberty, 

            J. Phys. Chem. A 106, 5043 (2002) 

94) Methyl Substituent Effects in [HnX\XHn]+ Three-Electron-Bonded Radical Cations (X= F, O; N, Cl, S, P; n=1-3). An ab initio Theoretical Study, B. Braïda, S. Hazebroucq et P.C. Hiberty, 

            J. Amer. Chem. Soc., 124, 2371 (2002) 

93) Alkoxy Radical Decomposition Explained by a Valence Bond Model, R. Mereau, M.T. Rayez, J.C. Rayez et P.C. Hiberty, 
Phys. Chem. Chem. Phys. 3, 3656 (2001).
92) Identity Hydrogen Abstraction Reactions, X + H-X' -> X-H + X' (X=X' = CH3, SiH3, GeH3, SnH3, PbH3): A Valence Bond Modeling, S. Shaik, W. Wu, K. Dong, L. Song and P.C. Hiberty, 

             J. Phys. Chem. A 105, 8226 (2001). 

91) Symmetry-Breaking and Near-Symmetry-Breaking in Three-Electron-Bonded Radical Cations, B. Braida, D. Lauvergnat et P.C. Hiberty, 

             J. Chem. Phys. 115, 90 (2001). 

90) A Different Story of p-Delocalization- The distortivity of ? Electrons and its Chemical Manifestations, S. Shaik, A. Shurki, D. Danovitch et P.C. Hiberty, 

             Chem. Rev. 101, 1501-1539 (2001). 

89) The s-p Energy Separation in modern electronic Theory for Ground States of Conjugated Systems, K. Jug, P.C. Hiberty et S. Shaik, 

              Chem. Rev. 101, 1477-1500 (2001) 

88) Diatomic Halogen Anions and Related Three-Electron-Bonded Anion Radicals: Very Contrasted Performances of Møller-Plesset Methods in Symmetric vs Dissymetric Cases, B. Braïda et P.C. Hiberty, 

             J. Phys. Chem. A 104, 4628 (2000). 

87) ?-Bonding in Second and Third Row Molecules: Testing the Strength of Linus's Blanket, J.M. Galbraith, E. Blank, S. Shaik et P.C. Hiberty, 

             Chem. Eur. J. 6, 2425 (2000). 

86) Ortho, Meta and Para Diphosphabenzenes and their P2(C-H)4 valence isomers. An Ab Initio Theoretical Study, L. Colombet, F. Volatron, P. Maître et P.C. Hiberty, 

            J. Amer. Chem. Soc. 121, 4215 (1999). 

 85) Charge-Shift Bond in Group IVB Halides: A Valence Bond Study of MH3-Cl (M = C, Si, Ge, Sn, Pb) Molecules, A. Shurki, P.C. Hiberty et S. Shaik, 

            J. Amer. Chem. Soc. 121, 822 (1999). 

 84) Thinking and Computing Valence Bond in Organic Chemistry, P.C. Hiberty, 

            J. Mol. Struc. (Theochem) 451, 237 (1998). 

 83) A Systematic Failing of Current Density Functionals: Overestimation of Two-Center Three-Electron Bonding Energies, B. Braïda, P. C. Hiberty et A. Savin, 

            J. Phys. Chem. A,102, 7872 (1998). 

 82) F4+: A Stable Three-Electron Bonded Complex and a Challenge for Standard Ab Initio Computational Methods, P.C. Hiberty et N. Berthe-Gaujac, 

            J. Phys. Chem. A,102, 3169 (1998). 

81) On the Suggestion of a Heteronuclear C\O Through-space Three-electron Bond in Tetrahydropyran Radical, S. Humbel et P.C. Hiberty, 

            J. Mol. Struc. (Theochem) 424, 57 (1998). 
 

Chapitres de livres:
 
1) P.C. Hiberty, "Analysis of MO-CI wavefunctions in terms of Valence Bond structures", dans 
  Valence Bond Theory and Chemical Structure, D.J. Klein et N. Trinajstic, eds., Elsevier, Amsterdam, p. 221 (1990). 

 2) P.C. Hiberty, "The distortive tendencies of delocalized ?-electronic systems. Benzene, cyclobutadiene and related heteroannulenes", dans 
  Topics in Current Chemistry, Vol. 153, p. 29 (1990). 

 3) P.C. Hiberty et S.S. Shaik, "Curve crossing diagrams as general models for chemical reactivity and structure", dans 
  Theoretical Models of the Chemical Bond, Z.B. Maksic, ed., Springer-Verlag, Heidelberg, pp 269-322 (1991). 

 4) P.C. Hiberty, E. Noizet, P. Maître et G. Ohanessian, "A comparison of ab initio valence bond methods in terms of compactness and of qualitative description of the chemical bond", dans 
  Molecules in Sience and Biomedicine - Encomium for Linus Pauling, Z.B. Maksic and M.E. Maksic, eds., Ellis Horwood, New York, pp 267-280 (1991). 

 5) S. Shaik et P.C. Hiberty, "Curve Crossing VB Diagrams: A General Concept in Chemical Reactivity", dans 
  Advances in Quantum Chemistry, P.O. Löwdin, ed., Academic Press, New York, Vol. 26, pp 99-163 (1995). 

6) The Breathing Orbital Valence Bond Method, P. C. Hiberty, dans: 
  Modern Electronic Structure Theory and Applications in Organic Chemistry, E. R. Davidson ed., World Scientific, London, pp 289-367(1997).  


  

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