Full configuration interaction calculations of the second hyperpolarizabilities of the H4 model compound: summation-over-states analysis and interplay with diradical characters.

The second hyperpolarizability (γ) of the one-dimensional H(4) model compound has been calculated at the full configuration interaction level to describe its relationships with the diradical characters y(i) [the occupation numbers of the lowest unoccupied natural orbital (LUNO) + i] and the geometry. It is found that the system with intermediate y(0) ( = 0.527) and small y(1) ( = 0.178) exhibits the largest γ value [enhanced by a factor of 9 compared to that of a nearly closed-shell H(4) analog (y(0) = 0.099, y(1) = 0.029)], where both the outer H-H distances are slightly larger than the inner one. These results provide a molecular design guideline for enhancing and controlling the third-order nonlinear optical properties of singlet multiradical linear molecular systems such as multiradical organic aggregates, supermolecular systems, and extended metal atom chains.

[1]  Z. Su,et al.  Boron/nitrogen substitution of the central carbon atoms of the biphenalenyl diradical π dimer: a novel 2e-12c bond and large NLO responses. , 2011, Chemistry.

[2]  Byung Sun Lee,et al.  Neutral radical and singlet biradical forms of meso-free, -keto, and -diketo hexaphyrins(1.1.1.1.1.1): effects on aromaticity and photophysical properties. , 2011, Journal of the American Chemical Society.

[3]  Y. Shigeta,et al.  Origin of the enhancement of the second hyperpolarizabilities in open-shell singlet transition-metal systems with metal-metal multiple bonds , 2011 .

[4]  Y. Shigeta,et al.  Third-order nonlinear optical properties of open-shell supermolecular systems composed of acetylene linked phenalenyl radicals. , 2011, The journal of physical chemistry. A.

[5]  P. Limacher,et al.  On the effect of electron correlation on the static second hyperpolarizability of π conjugated oligomer chains. , 2011, The Journal of chemical physics.

[6]  K. Ruud,et al.  The first and second static electronic hyperpolarizabilities of zigzag boron nitride nanotubes. An ab initio approach through the coupled perturbed Kohn-Sham scheme. , 2011, The journal of physical chemistry. A.

[7]  Manthos G. Papadopoulos,et al.  Electronic and vibrational linear and nonlinear polarizabilities of Li@C60 and [Li@C60]+ , 2011, J. Comput. Chem..

[8]  S. M. Rothstein,et al.  Ground-state properties of LiH by reptation quantum Monte Carlo methods. , 2011, Physical chemistry chemical physics : PCCP.

[9]  Alexander Baev,et al.  Twisted π-system chromophores for all-optical switching. , 2011, Journal of the American Chemical Society.

[10]  Wei Zhao.  Four-Wave Mixing Measurement of Third-Order Nonlinear Susceptibilities of Length-Sorted Single-Walled Carbon Nanotubes , 2011 .

[11]  Y. Shigeta,et al.  Erratum to: (Hyper)polarizability density analysis for open-shell molecular systems based on natural orbitals and occupation numbers , 2011 .

[12]  Kenichi Hibino,et al.  Third-order nonlinear optical properties of a π-conjugated biradical molecule investigated by third-harmonic generation spectroscopy , 2010 .

[13]  M. Nakano,et al.  Giant electric field effect on the second hyperpolarizability of symmetric singlet diradical molecules. , 2010, The Journal of chemical physics.

[14]  M. Nakano,et al.  Alternating covalent bonding interactions in a one-dimensional chain of a phenalenyl-based singlet biradical molecule having Kekulé structures. , 2010, Journal of the American Chemical Society.

[15]  M. Nakano,et al.  Signature of multiradical character in second hyperpolarizabilities of rectangular graphene nanoflakes , 2010 .

[16]  Y. Tobe,et al.  Tetradehydrodinaphtho[10]annulene and its transformation into zethrene: A hitherto unknown dehydroannulene and a forgotten aromatic hydrocarbon , 2010 .

[17]  M. Nakano,et al.  Singlet Diradical Character from Experiment , 2010 .

[18]  Oleksandr Loboda,et al.  Linear and nonlinear optical properties of triphenylamine-functionalized C60: insights from theory and experiment. , 2010, Physical chemistry chemical physics : PCCP.

[19]  B. Champagne,et al.  Polarizabilities and second hyperpolarizabilities of hydrogen chains using the spin-component-scaled Møller–Plesset second-order method† , 2009 .

[20]  L. Serrano-Andrés,et al.  Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives. , 2009, The Journal of chemical physics.

[21]  N. Marzari,et al.  Linear and nonlinear susceptibilities from diffusion quantum Monte Carlo: application to periodic hydrogen chains. , 2009, The Journal of chemical physics.

[22]  Yair Kurzweil Martin Head-Gordon.  Improving approximate-optimized effective potentials by imposing exact conditions: Theory and applications to electronic statics and dynamics , 2009, 0905.1260.

[23]  J. Perry,et al.  A new class of cyanine-like dyes with large bond-length alternation. , 2009, Journal of the American Chemical Society.

[24]  Prakash Chandra Jha,et al.  Spin multiplicity dependence of nonlinear optical properties. , 2009, Chemphyschem : a European journal of chemical physics and physical chemistry.

[25]  Xuri Huang,et al.  Large static first and second hyperpolarizabilities dominated by excess electron transition for radical ion pair salts M2*+TCNQ*- (M=Li, Na, K). , 2009, Physical chemistry chemical physics : PCCP.

[26]  M. Nakano,et al.  Theoretical study of third-order nonlinear optical properties in square nanographenes with open-shell singlet ground states , 2008 .

[27]  Gulliver T. Dalton,et al.  Cubic nonlinear optical properties of platinum-terminated polyynediyl chains. , 2008, Inorganic chemistry.

[28]  J. Perdew,et al.  Simple charge-transfer model to explain the electrical response of hydrogen chains , 2008 .

[29]  M. Nakano,et al.  Theoretical study on second hyperpolarizabilities of singlet diradical square planar nickel complexes involving o-semiquinonato type ligands. , 2008, The journal of physical chemistry. A.

[30]  R. Armiento,et al.  Electrical response of molecular chains in density functional theory: Ultranonlocal response from a semilocal functional , 2008 .

[31]  V. Rao,et al.  Estimation of the first excitation energy in diradicaloid croconate dyes having absorption in the near infra red (NIR) : A DFT and SF-TDDFT study , 2008 .

[32]  Z. Su,et al.  Theoretical study on the relationship between spin multiplicity effects and nonlinear optical properties of the pyrrole radical (C4H4N.). , 2008, The journal of physical chemistry. A.

[33]  Jörg Kussmann,et al.  A density matrix-based method for the linear-scaling calculation of dynamic second- and third-order properties at the Hartree-Fock and Kohn-Sham density functional theory levels. , 2007, The Journal of chemical physics.

[34]  Koji Ohta,et al.  Relationship between third-order nonlinear optical properties and magnetic interactions in open-shell systems: a new paradigm for nonlinear optics. , 2007, Physical review letters.

[35]  Lei Huang,et al.  Large third-order optical nonlinearities of centrosymmetric squaraines with heterocyclic donor groups measured by femtosecond degenerate four-wave mixing technique , 2007 .

[36]  M. Nakano,et al.  Strong two-photon absorption of singlet diradical hydrocarbons. , 2007, Angewandte Chemie.

[37]  C. Hättig,et al.  Frequency-dependent nonlinear optical properties with explicitly correlated coupled-cluster response theory using the CCSD(R12) model. , 2007, The Journal of chemical physics.

[38]  V. Rao,et al.  Enhanced diradical nature in oxyallyl derivatives leads to near infra red absorption: a comparative study of the squaraine and croconate dyes using computational techniques. , 2007, The journal of physical chemistry. A.

[39]  K. Bhanuprakash,et al.  Origin of near-infrared absorption and large second hyperpolarizability in oxyallyl diradicaloids: a three-state model approach. , 2007, The journal of physical chemistry. A.

[40]  Hai-bo Ma,et al.  Static polarizability and second hyperpolarizability of closed- and open-shell pi-conjugated polymers. , 2007, The Journal of chemical physics.

[41]  M. Nakano,et al.  Second hyperpolarizabilities (γ) of open-shell singlet one-dimensional systems : Intersite interaction effects on the average diradical character and size dependences of γ , 2006 .

[42]  M. Nakano,et al.  Origin of the enhancement of the second hyperpolarizability of singlet diradical systems with intermediate diradical character. , 2006, The Journal of chemical physics.

[43]  M. Nakano,et al.  Second hyperpolarizabilities of polycyclic aromatic hydrocarbons involving phenalenyl radical units , 2006 .

[44]  Benoît Champagne,et al.  Second Hyperpolarizability (γ) of Singlet Diradical System: Dependence of γ on the Diradical Character , 2005 .

[45]  Qin Wu,et al.  Accurate polymer polarizabilities with exact exchange density-functional theory , 2003 .

[46]  Mark S. Gordon,et al.  The Parallel Implementation of a Full Configuration Interaction Program , 2003 .

[47]  Martin Head-Gordon,et al.  Characterizing unpaired electrons from the one-particle density matrix , 2003 .

[48]  Ernest R. Davidson,et al.  Distribution of effectively unpaired electrons , 2000 .

[49]  S. Peng,et al.  One-dimensional metal string complexes , 2000 .

[50]  M. Nakano,et al.  MANY-ELECTRON HYPERPOLARIZABILITY DENSITY ANALYSIS : APPLICATION TO THE DISSOCIATION PROCESS OF ONE-DIMENSIONAL H2 , 1997 .

[51]  D. M. Bishop.  Explicit nondivergent formulas for atomic and molecular dynamic hyperpolarizabilities , 1994 .

[52]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[53]  M. Nakano,et al.  A proposal of new organic third-order nonlinear optical compounds. Centrosymmetric systems with large negative third-order hyperpolarizabilities , 1993 .

[54]  M. Head‐Gordon,et al.  A fifth-order perturbation comparison of electron correlation theories , 1989 .

[55]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[56]  Kazuo Takatsuka,et al.  Distribution of odd electrons in ground-state molecules , 1978 .

[57]  K. Hirao,et al.  The Effect of Silyl and Phenyl Functional Group End Caps on the Nonlinear Optical Properties of Polyynes: A Long-Range Corrected Density Functional Theory Study , 2009 .

[58]  Brian J. Orr,et al.  Perturbation theory of the non-linear optical polarization of an isolated system , 1971 .