Ab initio DFT study of Z–E isomerization pathways of N–benzylideneaniline

The ground state properties and absorption spectra of N-benzylideneaniline (NBA) have been studied at the density functional (DFT) and at the time-dependent density functional (TD-DFT) level of the theory. The equilibrium geometries of the E and Z isomers in the ground state and their vibrational frequencies have been computed. Furthermore, the excitation energies of the lowest excited singlet and triplet states and the potential energy curves along the torsion and the inversion isomerization coordinates were evaluated. The results are discussed in light of the available experimental data.

[1]  P. Dirac.  Quantum Mechanics of Many-Electron Systems , 1929 .

[2]  G. B. Kistiakowsky,et al.  Kinetics of Thermal Cis-Trans Isomerization. III , 1934 .

[3]  J. C. Slater.  A Simplification of the Hartree-Fock Method , 1951 .

[4]  E. Fischer,et al.  Photoisomerization Equilibria Involving the C=N Double Bond , 1957 .

[5]  P. Brocklehurst.  The ultra-violet spectra of azomethines and related compounds , 1962 .

[6]  E. Fischer.  Calculation of photostationary states in systems A .dblarw. B when only A is known , 1967 .

[7]  E. Heilbronner,et al.  Elektronenstruktur und physikalisch‐chemische Eigenschaften von Azo‐Verbindungen. Teil XIV: Die Konformation des Benzalanilins , 1968 .

[8]  J. Dunitz,et al.  Crystal and Molecular Structures of Benzylideneaniline, Benzylideneaniline‐p‐carboxylic acid and p‐methylbenzylidene‐p‐nitroaniline , 1970 .

[9]  V. Gil,et al.  The conformation of benzalanilines studied by NMR , 1971 .

[10]  M. El-Aasser,et al.  Electronic spectra and structures of Schiff's bases. I. Benzanils , 1971 .

[11]  J. Bernstein,et al.  Conformational studies. Part IV. Crystal and molecular structure of the metastable form of N-(p-chlorobenzylidene)-p-chloroaniline, a planar anil , 1972 .

[12]  H. Wendt,et al.  Investigations of the cis‐trans‐Isomerization of Benzylidene Aniline II. Kinetic Parameters of the cis‐trans‐Isomerization in Different Solvents [1] , 1972 .

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

[14]  G. Granneman,et al.  Cis-trans isomerism in the pyridyl analogs of azobenzene. Kinetic and molecular orbital analysis , 1975 .

[15]  M. Strauss,et al.  Benzomorphans: synthesis, stereochemistry reactions, and spectroscopic characterizations , 1977 .

[16]  E. Fischer,et al.  Photoformation of “Z” (cis) Isomers in Diaryl‐ and Triaryl‐ Azomethines, Part II.1 Electronic and NMR Spectra of Methyl Derivatives of Benzylideneaniline (C6H5—CH=N—C6H5) , 1977 .

[17]  A. Padwa.  Photochemistry of the carbon-nitrogen double bond , 1977 .

[18]  R. J. Abraham,et al.  The molecular structure of N-benzylidene-aniline , 1978 .

[19]  K. Tokumaru,et al.  Electronic Structures and Conformations of N-Benzylideneanilines. I. Electronic Absorption Spectral Study Combined with CNDO/S CI Calculations , 1980 .

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

[21]  A. Hagler,et al.  An ab initio study of the conformational energetics of N‐benzylideneaniline , 1981 .

[22]  L. N. Patnaik,et al.  Conformation of p‐dimethylaminobenzylidene‐p‐nitroaniline, p‐nitrobenzylidene‐p‐dimethylaminoaniline, their stilbene and azobenzene derivatives , 1985 .

[23]  Axel D. Becke,et al.  Density Functional Calculations of Molecular Bond Energies , 1986 .

[24]  J. Perdew,et al.  Density-functional approximation for the correlation energy of the inhomogeneous electron gas. , 1986, Physical review. B, Condensed matter.

[25]  Toshinori Suzuki,et al.  Two-color stimulated emission spectroscopy of trans-stilbene: large amplitude torsional motion in the ground state and its role in intramolecular vibrational redistribution , 1986 .

[26]  L. Spangler,et al.  Assignment of the low-frequency modes in trans-stilbene. Evidence for planarity in the isolated molecule , 1987 .

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

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

[29]  G. Baranović,et al.  Vibrational spectra of trans-N-benzylideneaniline and its isotopomers , 1989 .

[30]  R. Henderson,et al.  Model for the structure of bacteriorhodopsin based on high-resolution electron cryo-microscopy. , 1990, Journal of molecular biology.

[31]  E. Fischer,et al.  Reversible photochemistry of 4-nitro-substituted diphenylazomethines , 1991 .

[32]  M. El-Sayed.  On the molecular mechanisms of the solar to electric energy conversion by the other photosynthetic system in nature, bacteriorhodopsin , 1992 .

[33]  E. V. Titov,et al.  Interpretation of the vibrational spectrum of benzylideneaniline , 1993 .

[34]  R. Cimiraglia,et al.  Mechanism of Thermal Z/E Isomerization of Substituted N-Benzylideneanilines. Nature of the Activated Complex with an sp-Hybridized Nitrogen Atom , 1993 .

[35]  J. Laane,et al.  Fluorescence spectra and torsional potential functions for trans‐stilbene in its S0 and S1(π,π*) electronic states , 1994 .

[36]  Anil Kumar Singh,et al.  BATHOCHROMICITY OF RETINAL SCHIFF BASES IN CELLULOSE MATRIX , 1994 .

[37]  R. Ahlrichs,et al.  Efficient molecular numerical integration schemes , 1995 .

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

[39]  R. Ahlrichs,et al.  Treatment of electronic excitations within the adiabatic approximation of time dependent density functional theory , 1996 .

[40]  Florian Weigend,et al.  Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials , 1997 .

[41]  M. C. Flipse,et al.  Second-order nonlinear optical properties of stilbene,benzylideneaniline and azobenzene derivatives. The effect of π-bridgenitrogen insertion on the first hyperpolarizability , 1997 .

[42]  B. Roos,et al.  Theoretical Study of the Lowest 1BU States of trans-Stilbene , 2002 .

[43]  Filipp Furche,et al.  Adiabatic time-dependent density functional methods for excited state properties , 2002 .

[44]  F. Bernardi,et al.  On the mechanism of the cis-trans isomerization in the lowest electronic states of azobenzene: S0, S1, and T1. , 2004, Journal of the American Chemical Society.

[45]  F. Bernardi,et al.  A theoretical study of the lowest electronic states of azobenzene: the role of torsion coordinate in the cis–trans photoisomerization , 2004 .

[46]  A. Credi,et al.  Cyclohexenylphenyldiazene: a simple surrogate of the azobenzene photochromic unit. , 2007, Journal of the American Chemical Society.