Ab Initio Computations of Polarizabilities and Hyperpolarizabilities of Atoms and Molecules

Hasanein, Ahmed A.

doi:10.1002/9780470141441.ch6

Cited by 25 publications

(6 citation statements)

References 437 publications

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“…Table IV summarizes the intrinsic (static) dipole polarizabilities (α's) of the monomers and dimers, a response property that is expected to be important in electrostatic interactions. As can be seen, there is a good agreement of the values of α obtained from various levels of theory for the proton donors and best values of α are those obtained from the PBE and PW91 levels, which matches excellently well with the experimentally observed values 5.58, 16.97 36, and 23.50 37 a.u. for HF, HCl and HBr, respectively.…”

Section: Resultssupporting

confidence: 79%

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Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

Varadwaj

2006

Int J of Quantum Chemistry

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Linear hydrogen bonding formed between the nitrogen end of cyanogen-N-oxide (ONCCN) and hydrogen halides HX (X = F, Cl, Br) has been observed in their ground states. The order of agreement of energetic stabilities between the correlated functionals used in this calculation is: B3LYP < PBE0 < PBE < PW91 in conjunction with the 6-311++G(3df , 3pd) basis set. Analysis of various parameters describing the existence of H-bonds in these dimers follows the conventional trend: ONCCN · · ·HF > ONCCN · · ·HCl > ONCCN · · ·HBr in the series, except H-bond lengths and static dipole polarizabilities which are in reverse order. The atomic charges obtained from the Mulliken and natural population analysis is used to assess the charge transfer effects that accompany the dimer formation. It is found from the investigation that the dimers having highest binding energy are accompanied by the highest transfer of charge. The 14 N nuclear quadrupole coupling constants of the monomer ON 1 CCN 2 are found to be decreased upon complection and in the series it increases from F through Br. We observed enhancements in the values of the dimer dipole moment and intrinsic dipole polarizabilities compared with the sum of the monomer values by intermolecular electrical interaction. Investigation reveals vibrational spectral shifts of HX and CN stretching modes similar to the conventional red-shifted H-bonded dimers; for the former case, the infrared band intensity increases significantly. Finally, the new vibrational modes originated from the intermolecular interaction are outlined.

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Section: Resultssupporting

confidence: 79%

“… d Experimental values of α of HF, HCl, and HBr are reported to be 5.58, 16.97 36, and 23.50 37 a.u, respectively. …”

Section: Resultsmentioning

confidence: 99%

Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

Varadwaj

2006

Int J of Quantum Chemistry

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“…A tight SCF convergence criterion was adopted to ensure the precision of the computed polarizability. We have justified of our computational strategy by computing the polarizabilities of a single Co atom and benzene molecule, which are 9.10 and 11.73 Å 3 , respectively, in reasonable agreement with the measured values of 9.99 and 10.54 Å 3 and the previously computed value of 10.09 Å 3 at the CCSD/aug-cc-pVQZ level for benzene. Neither experimental nor theoretical polarizability for the Co atom is available to our knowledge.…”

Section: Computational Methodologysupporting

confidence: 82%

Size- and Shape-Dependent Polarizabilities of Sandwich and Rice-Ball Co_nBz_mClusters from Density Functional Theory

et al. 2008

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The dipole polarizabilities of Co(n)Bz(m), (n, m = 1-4, m = n, n + 1) clusters are studied by means of an all-electron gradient-corrected density functional theory and finite field method. The dipole moments are relatively large for most of the clusters, implying their asymmetric structures. The total polarizability increases rapidly as cluster size, whereas the average polarizability shows "odd-even" oscillation with relatively large values at (n, n + 1). The polarizabilities exhibit clear shape-dependent variation, and the sandwich structures have systematically larger polarizability and anisotropy than the rice-ball isomers. The dipole polarizabilities are further analyzed in terms of the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap, ionization potential, and electron delocalization volume. We conclude that the polarizability variations are determined by the interplay between the geometrical and electronic properties of the clusters.

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“…The accurate ab initio predictions of the nonlinear optical properties of practically useful material have been investigated by Shelton and Rice 20. Furthermore, a number of studies have been made by various research groups to the construction of reliable algorithms and computational strategies for the prediction of reliable theoretical values 20–34. Maroulis 35 performed as a series of basis sets for hyperpolarizability calculations on molecules of the size and complexity of trans ‐butadiene.…”

Section: Introductionmentioning

confidence: 99%

“…Besides, the choice of the basis set is also a critical point in any computational study on molecular properties. To investigate the basis set effect on result, we take in to account eight types of basis functions: (i) 6‐31G, (ii) 6‐311G, (iii) 6‐31G(d), and (iv) 6‐311G(d) 23–25 for checking (d) polarization function effect, (v) 6‐31+G(d) and (vi) 6‐311+G(d) 23–25 for checking both (d) polarization function and + diffuse function effects, (vii) 6‐31++G(d,p) and (viii) 6‐311++G(d,p) 39–41 for checking both (d,p) polarization functions and ++ diffuse effects. We design 18 molecules based on heterocyclic 1,3,4‐oxadiazole moiety, and present ground‐state dipole moment (μ), the polarizability (<α>), anisotropy of polarizability (Δα) and first hyperpolarizability (β), the vector component of first hyperpolarizability (β vec ) and HOMO and LUMO energies of 5a – f , 8a – f , and 9a – f using the Hartree‐Fock and B3LYP methods with 6‐31G, 6‐31G(d), 6‐31+G(d), 6‐31++G(d,p), 6‐311G, 6‐311G(d), 6‐311+G(d), and 6‐311++G(d,p) basis sets have been investigated.…”

Section: Introductionmentioning

confidence: 99%

Effects of different basis sets and donor‐acceptor groups on linear and second‐order nonlinear optical properties and molecular frontier orbital energies

Avcı

Başoğlu

Atalay

2010

Int J of Quantum Chemistry

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ABSTRACT:The calculation of molecular hyperpolarizability, molecular frontier orbital energies of some donor-acceptor oxadiazoles (5a-f, 8a-f, and 9a-f) have been investigated using ab initio methods and different basis sets. Ab initio optimizations were performed at the Hartree-Fock (HF) and density functional (Beckee-3-Lee-YangParr; B3LYP) levels of theory with 6-31G basis set. The polarizability (Ͻ␣Ͼ), anisotropy of polarizability (⌬␣), and ground-state dipole moment (), first hyperpolarizability (␤), and molecular frontier orbital (HOMO, highest occupied molecular orbital and LUMO, lowest unoccupied molecular orbital) energies of 5a-f, 8a-f, and 9a-f have been calculated at the HF and B3LYP methods with 6-31G, 6-31G(d), 6-31ϩG(d), 6-31ϩϩG(d,p), 6-311G, 6-311G(d), 6-311ϩG(d), and 6-311ϩϩG(d,p) basis sets. Also, the molecular hardness () and electronegativity () parameters have been obtained using molecular frontier orbital energies. The Ͻ␣Ͼ, ⌬␣, , ␤, HOMO, LUMO energies, and parameters have been investigated as dependence on the choice of method and basis set. The variation graphics of Ͻ␣Ͼ, ⌬␣, , ␤, , and parameters using HF and B3LYP methods with different basis sets are presented. We have examined the frontier molecular orbital pictures of 5a-f, 8a-f, and 9a-f using B3LYP/6-31ϩϩG(d,p) level. The 5a-f, 8a-f, and 9a-f display significant linear, second-order molecular nonlinearity, and molecular parameters and provide the basis for future design of efficient nonlinear optical materials having the 1,3,4-oxadiazole core.

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Ab Initio Computations of Polarizabilities and Hyperpolarizabilities of Atoms and Molecules

Cited by 25 publications

References 437 publications

Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

Size- and Shape-Dependent Polarizabilities of Sandwich and Rice-Ball Co_nBz_mClusters from Density Functional Theory

Effects of different basis sets and donor‐acceptor groups on linear and second‐order nonlinear optical properties and molecular frontier orbital energies

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Ab Initio Computations of Polarizabilities and Hyperpolarizabilities of Atoms and Molecules

Cited by 25 publications

References 437 publications

Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

Quantum chemical investigation of linear hydrogen bonding in ONCCN···HX (X = F, Cl, Br) dimers

Size- and Shape-Dependent Polarizabilities of Sandwich and Rice-Ball ConBzmClusters from Density Functional Theory

Effects of different basis sets and donor‐acceptor groups on linear and second‐order nonlinear optical properties and molecular frontier orbital energies

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Size- and Shape-Dependent Polarizabilities of Sandwich and Rice-Ball Co_nBz_mClusters from Density Functional Theory