Cumulative atomic multipole representation of the molecular charge distribution and its basis set dependence

Sokalski, W. Andrzej; Poirier, Raymond A.

doi:10.1016/0009-2614(83)80208-5

Cited by 196 publications

(109 citation statements)

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“…Mulliken charges and the associated CAMM atomic moments are arbitrary and often strongly basis set dependent [9], but the plotted changes in atomic charges illustrate the magnitude of charge redistribution and should be less sensitive (Löwdin charges were compared in this case). If anything, these changes pinpoint which atoms participate in the reaction and in which direction the flow of charge takes place.…”

Section: Charge Redistribution Along a Reaction Pathmentioning

confidence: 99%

“…One way to improve this it to employ atomic dipoles and higher moments to describe local deviations from an isotropic distribution. Again, this can be implemented as an extension of population analyses using schemes such as distributed multipole analysis (DMA) [8] and cumulative atomic multipole moments (CAMM) [9,10], or fitted along with atomic charges (monopoles) to a surrounding electrostatic potential [11][12][13]. In the present contribution, we look at the ability of atomic multipole moments obtained using the CAMM scheme to reproduce the molecular electrostatic potentials on the solvent-excluded surface around five reactions involving both neutral and charged reactants.…”

Section: Introductionmentioning

confidence: 99%

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Tracking molecular charge distribution along reaction paths with atomic multipole moments

et al. 2016

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We explore the idea of supplementing partial atomic charges with cumulative multipole moments for modeling electrostatic effects during chemical reactions.To this end, we investigate the first stage of alkaline hydrolysis of O,O-dimethyl phosphorofluoridate and show how changes in atomic moments provide a more detailed description of charge redistribution during the reaction than is possible using charges alone. Furthermore, the electrostatic potential on the solvent-excluded surface for this reaction roughly converges at the quadrupolar level, with a root-mean-square deviation of *1 kcal/mol compared to the ab initio Hartree-Fock expectation value. We arrive at similar conclusions for four other reactions, namely the alkaline hydrolysis of demeton-S and phosalone, carbon dioxide hydration, and hydrogen cyanide isomerization. Employing multipole moments on atoms therefore appears to be a feasible and compact way to derive catalytic fields defining the optimal catalytic environment for chemical reactions.

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Section: Charge Redistribution Along a Reaction Pathmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Tracking molecular charge distribution along reaction paths with atomic multipole moments

et al. 2016

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“…Like many authors in this field, [21][22][23] we give to each atom a set of multipoles. The matrix elements are expressed as a function…”

Section: Reference Points Generationmentioning

confidence: 99%

A diabatic parameterization of the twofold ground state potential energy surface of the H2O-OH molecular complex

Galbis

Giglio

Gervais

2013

The Journal of Chemical Physics

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Correlated ab initio investigations on the intermolecular and intramolecular potential energy surfaces in the ground electronic state of the O 2 − ( X Π g 2 ) − HF ( X Σ + 1 ) complex J. Chem. Phys. 138, 014304 (2013) We present a matrix functional form to fit the nearly degenerated potential energy surface of the H 2 O-OH molecular complex. The functional form is based on second order perturbation theory, which allows us to define two diabatic states coupled together in the field of the surrounding water molecules. The fit reproduces faithfully the fine details of the potential energy surface (PES) like the crossings and the shallow barrier between the main and secondary minima. The explicit dependence of the model on polarization ensures its transferability to systems made of several water molecules. The potential is used to investigate the structural properties of the OH radical in solution by Monte Carlo simulation. The twin surface fit shows that the second PES is shifted above the ground state by typically 1600 cm −1 for the configurations explored at a temperature of 300 K and a density of 1.0 g/cm 3 . The second PES has thus little influence on the structuring of water around the OH radical at such a temperature and density. Our study confirms that under these thermodynamic conditions, OH is a weak hydrogen acceptor.

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“…); Z a is nuclear charge; r u k v l w m s is socalled multipole integral over atomic orbitals r, s; and the last term subtracts from m klm a the contribution described by lower-order multipole moments [5].…”

Section: The Cumulative Atomic Multipole Momentsmentioning

confidence: 99%

“…The visualization was implemented using scripting interface of VMD [3]. Cumulative Atomic Multipole Moments (CAMM) [4,5,6] were utilized for efficient yet accurate evaluation of the electrostatic properties. The implementation is efficient enough for interactive presentation of catalytic effects in the active site of the enzyme due to transition state or substrate movement.…”

Section: Introductionmentioning

confidence: 99%

Visualization of the Differential Transition State Stabilization within the Active Site Environment

Kędzierski

Wielgus

Sikora

et al. 2004

IJMS

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Abstract:Increasing interest in the enzymatic reaction mechanisms and in the nature of catalytic effects in enzymes causes the need of appropriate visualization methods. A new interactive method to investigate catalytic effects using differential transition state stabilization approach (DTSS) [1, 2] is presented. The catalytic properties of the active site of cytidine deaminase (E.C. 3.5.4.5) is visualized in the form of differential electrostatic properties. The visualization was implemented using scripting interface of VMD [3]. Cumulative Atomic Multipole Moments (CAMM) [4,5,6] were utilized for efficient yet accurate evaluation of the electrostatic properties. The implementation is efficient enough for interactive presentation of catalytic effects in the active site of the enzyme due to transition state or substrate movement. This system of visualization of DTTS approach can be potentially used to validate hypotheses regarding the catalytic mechanism or to study binding properties of transition state analogues.

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Cumulative atomic multipole representation of the molecular charge distribution and its basis set dependence

Cited by 196 publications

References 19 publications

Tracking molecular charge distribution along reaction paths with atomic multipole moments

Tracking molecular charge distribution along reaction paths with atomic multipole moments

A diabatic parameterization of the twofold ground state potential energy surface of the H2O-OH molecular complex

Visualization of the Differential Transition State Stabilization within the Active Site Environment

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