Density functional studies of molecular polarizabilities.

Hinchliffe, Alan; Machado, Humberto J. Soscún

doi:10.1016/s0009-2614(00)00319-5

Cited by 18 publications

(16 citation statements)

References 5 publications

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“…The derivatives have been evaluated by using the finite field method [48,[65][66][67]. The mean polarisability (ᾱ) is calculated from the diagonal elements of the polarisability tensor asᾱ…”

Section: Methodsmentioning

confidence: 99%

Hydrogen-bonded glycine–HCN complexes in gas phase: structure, energetics, electric properties and cooperativity

2014

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Twelve hydrogen-bonded complexes of glycine and hydrogen cyanide have been studied using high-level quantum-chemical calculations in gas phase. In particular, six 1:1 glycine-HCN dimers and six 1:2 glycine-HCN trimers have been considered. Besides the characteristics of the hydrogen bonds and their effect on molecular structure and energetics, several molecular electric properties have been calculated utilising two different models: MP2/6-31 ++ G(d,p) and DFT-B3LYP/6-31 ++ G(d,p). Although the structural parameters calculated by the two models are similar, equilibrium electronic energies of the clusters show model dependence. The lowest energy dimer is same in both the models which is ca. 3.0 kcal/mol more stable than the highest energy dimer. However, the lowest energy trimer is different in two methods. The energetic difference of stability between the highest and lowest trimer is 4.2 kcal/mol (4.4 kcal/mol) at an MP2 (B3LYP) level of calculation. The bond angles of glycine, in particular, are quite sensitive to the hydrogen-bond formation. Four out of six trimers are found to be strongly cooperative in both the models. Significant changes of dipole moments and polarisabilities of isolated glycine and hydrogen cyanide are observed due to the formation of hydrogen bonding. The Rayleigh scattering intensities of all clusters are much larger than those of their constituent monomers.

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Section: Methodsmentioning

confidence: 99%

Hydrogen-bonded glycine–HCN complexes in gas phase: structure, energetics, electric properties and cooperativity

2014

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“…In addition, previous literature show that the predictive capability of the B3LYP functional for electronic polarizability is fair [45,46] and even better than MP2 method in some case [47]. Having the optimized structure, the frequency independent (static) dipole polarizabilities ðãÞ, and first order hyperpolarizabilities (b) are calculated with B3LYP functional using the finite field method [48][49][50][51]. The calculations of the hyperpolarizabilities require flexible and adequately polarized and diffuse added basis set.…”

Section: Methodsmentioning

confidence: 99%

Structure and NLO properties of halogen (F, Cl) substituted formic acid dimers

Umadevi

Senthilkumar

Gayathri

et al. 2014

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…All calculations were carried out using the computational package GAUSSIAN 03 31. Having the optimized structures, the static (frequency‐independent) dipole polarizabilities are calculated using the finite‐field method,3, 32–34 as discussed briefly below.…”

Section: Methodsmentioning

confidence: 99%

“…The presence of the external electric field of an incident light wave may induce oscillating electric moments in a molecular system. Thus, the molecular charge density may rearrange, the dipole moment may change,32 and the molecule may suffer distortions because of the applied field. This change can be expressed conveniently as Taylor expansion of the permanent electric dipole moment, μ p with respect to the applied electric field, E : \font\abc=cmmib10\def\bi #1{\hbox{\abc #1}} $$ \mu _{{\rm{p}},j} ({\bi E}) = \mu _{{\rm{p}},j} ({\bi 0}) + \sum\limits_{j = x}^z {\alpha _{ij} E_j } + {1 \over 2}\sum\limits_{j = x}^z {\sum\limits_{k = x}^z {\beta _{ijk} } } E_j E_k + \cdots $$ …”

Section: Methodsmentioning

confidence: 99%

Rayleigh light scattering from hydrogen‐bonded dimers of small astrophysical molecules

Silva

Chakraborty

Chaudhuri

2011

Int J of Quantum Chemistry

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High level ab initio calculations of the Rayleigh scattering activities of the hydrogen-bonded dimers of formic acid (HCOOH), nitrosyl hydride (HNO), and hydrogen cyanide (HCN) molecules have been performed. All these molecules have already been detected in interstellar space and are of great importance from the astrochemical point of view. The geometries of the homo-and hetero-dimers have been optimized using Hartree-Fock and second-order Møller-Plesset perturbation theory. Dipole moment, mean dipole polarizability, and polarizability anisotropy have been calculated utilizing Pople-type 6-311þþG(d,p) and Dunning's aug-cc-pVDZ basis sets for all the complexes. The polarizabilities are then used to calculate and analyze the Rayleigh scattering parameters. The results for the dimers, HCNÁÁÁHCN, HCOOHÁÁÁHCOOH, HNOÁÁÁHNO, HCNÁÁÁHCOOH, HCNÁÁÁHNO, and HNOÁÁÁHCOOH are compared with those of the isolated molecules, HCN, HCOOH, and HNO to see the effect of hydrogen bond formation on the molecular interaction with radiation.

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Density functional studies of molecular polarizabilities.

Cited by 18 publications

References 5 publications

Hydrogen-bonded glycine–HCN complexes in gas phase: structure, energetics, electric properties and cooperativity

Hydrogen-bonded glycine–HCN complexes in gas phase: structure, energetics, electric properties and cooperativity

Structure and NLO properties of halogen (F, Cl) substituted formic acid dimers

Rayleigh light scattering from hydrogen‐bonded dimers of small astrophysical molecules

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