Validity of the Minimum Polarizability Principle in Molecular Vibrations and Internal Rotations:  An ab Initio SCF Study

Chattaraj, Pratim Kumar; Fuentealba, Patricio; Jaque, Pablo; Toro–Labbé, Alejandro

doi:10.1021/jp9918656

Cited by 132 publications

(108 citation statements)

References 18 publications

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“…However, relaxation of these constraints seems to be permissible, and in particular, it has been found that in most cases the MHP still holds even though the chemical and external potentials vary during the molecular vibration, internal rotation or along the reaction coordinate. 12,[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33] Hereafter, we will refer to the generalized MHP ͑GMHP͒ or MPP ͑GMPP͒ as the maximum hardness or minimum polarizability principles that do not require the constancy of chemical and external potentials during molecular change. It is worth emphasizing that the generalized versions of these principles have not been proven.…”

Section: Introductionmentioning

confidence: 99%

“…11 As a consequence, the MHP and MPP are expected to be obeyed for nontotally symmetric vibrations, as confirmed by most numerical calculations of hardness and polarizability along the nontotally symmetric normal modes performed so far. 9,[15][16][17][18] For totally symmetric distorsions, the situation is drastically different. Now, starting from the equilibrium geometry the hardness keeps increasing steadily as the nuclei approach each other.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

Torrent‐Sucarrat

Luis

Duran

et al. 2002

The Journal of Chemical Physics

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In a recent paper ͓J. Am. Chem. Soc. 123, 7951 ͑2001͔͒ we have shown for the first time the existence of molecules with nontotally symmetric vibrational modes that break the maximum hardness ͑MHP͒ and minimum polarizability ͑MPP͒ principles. We present here an extension of this previous work by devising a mathematical procedure that helps to determine the nontotally symmetric molecular distortions of a given molecule that do not follow the MPP or the MHP. This methodology is based on the diagonalization of the Hessian matrix of the polarizability or the hardness with respect to the vibrational normal coordinates. For a relatively large series of molecules, we have carried out diagonalizations of the Hessian matrix of the polarizability to determine the molecular distortions with a more marked MPP or anti-MPP character. From the results obtained, we have derived a set of simple rules that allow to predict a priori without calculations the existence of vibrational modes that break the MPP. With respect to the MHP, the results strongly depend on the method of calculation, but the same rules are useful to predict the existence of vibrational modes that disobey the MHP when the Koopmans' approximation is used to calculate the hardness.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

Torrent‐Sucarrat

Luis

Duran

et al. 2002

The Journal of Chemical Physics

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“…In this way, all electronic structures down to the amino acid levels and even to individual atoms within the amino acids can be displayed. According to the principle of maximum hardness (PMH) [69,70], the HOMO-LUMO gap (ε LUMO − ε HOMO ) can be related to maximum hardness η = ½ (ε LUMO − ε HOMO ) and used to roughly estimate the stability of each molecular fragment [71,72]. Based on this simple rule, the fifth trimer (Gly-Ala-Ala) and the sixth trimer (Gly-Ala-Hyp) in the middle part of the α 2 (I) chain should be more stable than the other trimers.…”

Section: Results and Discussion On The Collagen Modelmentioning

confidence: 99%

Computational Study of a Heterostructural Model of Type I Collagen and Implementation of an Amino Acid Potential Method Applicable to Large Proteins

et al. 2014

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Collagen molecules are the primary structural proteins of many biological systems. Much progress has been made in the study of the structure and function of collagen, but fundamental understanding of its electronic structures at the atomic level is still lacking. We present the results of electronic structure and bonding calculations of a specific model of type I collagen using the density functional theory-based method. Information on density of states (DOS), partial DOS, effective charges, bond order values, and intra-and inter-molecular H-bonding are obtained and discussed. We further devised an amino-acid-based potential method (AAPM) to circumvent the full self-consistent field (SCF) calculation that can be applied to large proteins. The AAPM is validated by comparing the results with the full SCF calculation of the whole type I collagen model with three strands. The calculated effective charges on each atom in the model retained at least 95% accuracy. This technique provides a viable and efficient way to study the electronic structure of large complex biomaterials at the ab initio level.

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“…63 The minima and maximum of hardness indicate the presence of two transition states and an equilibrium structure, respectively. Then, the number of the stationary points in the energy and hardness profiles is the same.…”

Section: H 2 Omentioning

confidence: 99%

The hardness profile as a tool to detect spurious stationary points in the potential energy surface

Torrent‐Sucarrat

Luis

Duran

et al. 2004

The Journal of Chemical Physics

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In the present work, we have computed the energy and hardness profiles for a series of inter and intramolecular conformational changes at several levels of calculation. All processes studied have in common the fact that the choice of a weak methodology or a poor basis set results in the presence of spurious stationary points in the energy profile. At variance with the energy profiles, the hardness profiles calculated as the difference between the vertical ionization potential and electron affinity always show the correct number of stationary points independently of the basis set and methodology used. For this reason, we have concluded that hardness profiles can be used to check the reliability of the energy profiles for those chemical systems that, because of their size, cannot be treated with high level ab initio methods.

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Validity of the Minimum Polarizability Principle in Molecular Vibrations and Internal Rotations: An ab Initio SCF Study

Cited by 132 publications

References 18 publications

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

Computational Study of a Heterostructural Model of Type I Collagen and Implementation of an Amino Acid Potential Method Applicable to Large Proteins

The hardness profile as a tool to detect spurious stationary points in the potential energy surface

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