Development and Validation of the B3LYP/N07D Computational Model for Structural Parameter and Magnetic Tensors of Large Free Radicals.

Extensive calculations on a large set of free radicals containing atoms of the second and third row show that the B3LYP/N07D computational model provides remarkably accurate structural parameters and magnetic tensors at reasonable computational costs. The key of this success is the optimization of core-valence s functions for hyperfine coupling constants, while retaining (and even improving) the good performances of the parent 6-31+G(d,p) basis set for valence properties through reoptimization of polarization and diffuse p functions.

[1]  V. Barone,et al.  Accurate and feasible computations of structural and magnetic properties of large free radicals : The PBE0/N07D model , 2008 .

[2]  V. Barone,et al.  Unraveling the role of stereo-electronic, dynamical, and environmental effects in tuning the structure and magnetic properties of glycine radical in aqueous solution at different pH values. , 2007, Journal of the American Chemical Society.

[3]  A. Polimeno,et al.  Integrated computational strategies for UV/vis spectra of large molecules in solution. , 2007, Chemical Society reviews.

[4]  Takao Tsuneda,et al.  Long-range corrected density functional study on weakly bound systems: balanced descriptions of various types of molecular interactions. , 2007, The Journal of chemical physics.

[5]  S. Kacprzak,et al.  Understanding the EPR parameters of glycine-derived radicals: the case of N-acetylglycyl in the N-acetylglycine single-crystal environment. , 2007, The journal of physical chemistry. B.

[6]  V. Barone,et al.  Theoretical modeling of spectroscopic properties of molecules in solution: toward an effective dynamical discrete/continuum approach , 2007 .

[7]  S. Mattar.  Accurate calculation of the phenyl radical's magnetic inequivalency, relative orientations of its spin hamiltonian tensors, and its electronic spectrum. , 2007, The journal of physical chemistry. A.

[8]  L. Hermosilla,et al.  Density functional theory study of 14N isotropic hyperfine coupling constants of organic radicals. , 2006, The journal of physical chemistry. A.

[9]  P. Cummings,et al.  Hydrogen bonding and induced dipole moments in water: predictions from the Gaussian charge polarizable model and Car-Parrinello molecular dynamics. , 2006, The Journal of chemical physics.

[10]  Hans-Joachim Werner,et al.  Calculation of intermolecular interactions in the benzene dimer using coupled-cluster and local electron correlation methods. , 2006, Physical chemistry chemical physics : PCCP.

[11]  O. Christiansen.  Coupled Cluster Theory with Emphasis on Selected New Developments , 2006 .

[12]  Jirí Cerný,et al.  Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs. , 2006, Physical chemistry chemical physics : PCCP.

[13]  Vincenzo Barone,et al.  Interplay of stereoelectronic and enviromental effects in tuning the structural and magnetic properties of a prototypical spin probe: further insights from a first principle dynamical approach. , 2006, Journal of the American Chemical Society.

[14]  Donald G Truhlar,et al.  Design of Density Functionals by Combining the Method of Constraint Satisfaction with Parametrization for Thermochemistry, Thermochemical Kinetics, and Noncovalent Interactions. , 2006, Journal of chemical theory and computation.

[15]  L. Hermosilla,et al.  Theoretical isotropic hyperfine coupling constants of third-row nuclei (29Si, 31P, and 33S). , 2005, The journal of physical chemistry. A.

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

[17]  Frank Neese,et al.  Toward identification of the compound I reactive intermediate in cytochrome P450 chemistry: a QM/MM study of its EPR and Mössbauer parameters. , 2005, Journal of the American Chemical Society.

[18]  Vincenzo Barone,et al.  Solvent effects on the UV (n --> pi*) and NMR (13C and 17O) spectra of acetone in aqueous solution. An integrated car-parrinello and DFT/PCM approach. , 2005, The journal of physical chemistry. B.

[19]  Xin Huang,et al.  Metal ion modulated organization and function of the Langmuir-Blodgett films of amphiphilic diacetylene: photopolymerization, thermochromism, and supramolecular chirality. , 2005, The journal of physical chemistry. B.

[20]  M. Frisch,et al.  Effect of time-dependent basis functions and their superposition error on atom-centered density matrix propagation (ADMP): connections to wavelet theory of multiresolution analysis. , 2004, The Journal of chemical physics.

[21]  V. Barone.  Accurate Vibrational Spectra of Large Molecules by Density Functional Computations beyond the Harmonic Approximation: The Case of Azabenzenes , 2004 .

[22]  Xin Xu,et al.  From The Cover: The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[23]  V. Barone,et al.  Interplay of electronic, environmental, and vibrational effects in determining the hyperfine coupling constants of organic free radicals. , 2004, Chemical reviews.

[24]  R. Bartlett,et al.  Benchmark study of isotropic hyperfine coupling constants for hydrogen: Influence of geometry, correlation method, and basis set , 2003 .

[25]  C. Trapp,et al.  Fluorine Hyperfine Splittings in the Electron Spin Resonance (ESR) Spectra of Aromatic Radicals. An Experimental and Theoretical Investigation , 2003 .

[26]  F. Neese.  Metal and ligand hyperfine couplings in transition metal complexes: The effect of spin-orbit coupling as studied by coupled perturbed Kohn-Sham theory , 2003 .

[27]  Caterina Benzi,et al.  Quantum mechanical study of the conformational behavior of proline and 4R‐hydroxyproline dipeptide analogues in vacuum and in aqueous solution , 2002, J. Comput. Chem..

[28]  Brian J. Wright,et al.  Addition of Polarization and Diffuse Functions to the LANL2DZ Basis Set for P-Block Elements , 2001 .

[29]  G. Scuseria,et al.  Ab initio molecular dynamics: Propagating the density matrix with Gaussian orbitals , 2001 .

[30]  M. Halls,et al.  Harmonic frequency scaling factors for Hartree-Fock, S-VWN, B-LYP, B3-LYP, B3-PW91 and MP2 with the Sadlej pVTZ electric property basis set , 2001 .

[31]  G. Scuseria,et al.  Structure and conformational behavior of biopolymers by density functional calculations employing periodic boundary conditions. I. The case of polyglycine, polyalanine, and poly-alpha-aminoisobutyric acid in vacuo. , 2001, Journal of the American Chemical Society.

[32]  V. Barone,et al.  An accurate density functional method for the study of magnetic properties: the PBE0 model , 1999 .

[33]  P Hobza,et al.  Structure, energetics, and dynamics of the nucleic Acid base pairs: nonempirical ab initio calculations. , 1999, Chemical reviews.

[34]  R. J. Doerksen,et al.  Geometries and multipole moments of AlH4−, SiH4, PH3, H2S and HCl , 1999 .

[35]  Gustavo E. Scuseria,et al.  Linear Scaling Density Functional Calculations with Gaussian Orbitals , 1999 .

[36]  V. Barone,et al.  Toward reliable density functional methods without adjustable parameters: The PBE0 model , 1999 .

[37]  Mathew D. Halls,et al.  Comparison of the performance of local, gradient-corrected, and hybrid density functional models in predicting infrared intensities , 1998 .

[38]  V. Barone,et al.  Structure and Magnetic Properties of Glycine Radical in Aqueous Solution at Different pH Values , 1998 .

[39]  V. Barone,et al.  Intrinsic and Environmental Effects in the Structure and Magnetic Properties of Glycine Radical in Aqueous Solution , 1997 .

[40]  V. Barone,et al.  Development and validation of reliable quantum mechanical approaches for the study of free radicals in solution , 1996 .

[41]  J. Rustad,et al.  Molecular statics calculations for iron oxide and oxyhydroxide minerals: Toward a flexible model of the reactive mineral-water interface , 1996 .

[42]  V. Barone.  Structure, Thermochemistry, and Magnetic Properties of Binary Copper Carbonyls by a Density-Functional Approach , 1995 .

[43]  B. Engels,et al.  Multireference Configuration Interaction and Density Functional Study of the Azetidine Radical Cation and the Neutral Azetidin-1-yl Radical , 1995 .

[44]  V. Barone.  Structure, epr parameters, and reactivity of organic free radicals from a density functional approach , 1995 .

[45]  V. Barone.  CHARACTERIZATION OF THE POTENTIAL ENERGY SURFACE OF THE HO2 MOLECULAR SYSTEM BY A DENSITY FUNCTIONAL APPROACH , 1994 .

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

[47]  Rick A. Kendall,et al.  BENCHMARK CALCULATIONS WITH CORRELATED MOLECULAR WAVE FUNCTIONS. III: CONFIGURATION INTERACTION CALCULATIONS ON FIRST ROW HOMONUCLEAR DIATOMICS , 1993 .

[48]  V. Barone,et al.  Density functional approach to the structures and EPR parameters of open shell systems. The case of fluorovinyl radicals , 1993 .

[49]  Rick A. Kendall,et al.  Benchmark calculations with correlated molecular wave functions. II. Configuration interaction calculations on first row diatomic hydrides , 1993 .

[50]  Dennis R. Salahub,et al.  Optimization of Gaussian-type basis sets for local spin density functional calculations. Part I. Boron through neon, optimization technique and validation , 1992 .

[51]  Chipman,et al.  Spin densities of first-row atoms calculated from polarization wave functions with accurate numerical methods. , 1989, Physical review. A, General physics.

[52]  B. Engels,et al.  Study of the 1s and 2s shell contributions to the isotropic hyperfine coupling constant in nitrogen , 1988 .

[53]  Car,et al.  Unified approach for molecular dynamics and density-functional theory. , 1985, Physical review letters.

[54]  H. Werner,et al.  Theoretical dipole moment functions of the HF, HCl, and HBr molecules , 1980 .

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

[56]  Vincenzo Barone,et al.  Anharmonic vibrational properties by a fully automated second-order perturbative approach. , 2005, The Journal of chemical physics.

[57]  D. Robinson,et al.  Mid‐ and Far‐Infrared Spectra of HF and DF in Rare‐Gas Matrices , 1971 .