Correlated molecular and cumulative atomic multipole moments

Sokalski, W. Andrzej; Sawaryn, A.

doi:10.1063/1.453600

Cited by 104 publications

(47 citation statements)

References 63 publications

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“…[47][48][49] Similar conclusions were also drawn from the studies of supermolecular interaction energies in both hydrogen-bonded 50,51 and π-π interacting 52 systems, molecular electric moments and polarizabilities, 53 and so-called correlated cumulative atomic multipole moments. 54 Our results confirm that augmenting a given basis set is more important for the calculation of E es , and also E int , 52 than adding a shell of valence functions (i.e., aug-cc-pVDZ vs cc-pVTZ).…”

Section: Effect Of Inclusion Of Diffuse Functions In the Basis Setssupporting

confidence: 75%

Dependence of the Intermolecular Electrostatic Interaction Energy on the Level of Theory and the Basis Set

Volkov

King

Coppens

2005

J. Chem. Theory Comput.

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Abstract:As electrostatic forces play a prominent role in the process of folding and binding of biological macromolecules, an examination of the method dependence of the electrostatic interaction energy is of great importance. An extensive analysis of the basis set and method dependence of electrostatic interaction energies (E es ) in molecular systems using six test dimers of R-glycine is presented. A number of Hartree-Fock, Kohn-Sham, Møller-Plesset, configuration interaction (CI), quadratic CI, and coupled cluster calculations were performed using several double-, triple-, and quadruple--quality Gaussian-and Slater-type (Kohn-Sham calculations only) basis sets. The main factor affecting E es was found to be the inclusion of diffuse functions in the basis set expansions. Møller-Plesset (even at second order), quadratic CI, and coupled cluster calculations produce the most consistent results. Hartree-Fock and CI methods usually overestimate the E es , while the Kohn-Sham approach tends to underestimate the magnitude of the electrostatic interaction. The combination of the transferable-pseudoatom databank and the exact potential and multipole moment method reproduces Kohn-Sham B3LYP/6-31G** results on which it is based, confirming the excellent transferability of the pseudoatom densities within the systems studied. However, because Kohn-Sham calculations with double--quality basis sets show considerable deviations from advanced correlated methods, further development of the databank using electron densities from such methods is highly desirable.

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Section: Effect Of Inclusion Of Diffuse Functions In the Basis Setssupporting

confidence: 75%

Dependence of the Intermolecular Electrostatic Interaction Energy on the Level of Theory and the Basis Set

Volkov

King

Coppens

2005

J. Chem. Theory Comput.

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“…As with many methods requiring least-squares fitting of a complex function, artifacts were observed in this procedure that limited the transferability and accuracy of the charge model. 28 More examples of multicentered multipole expansions include Sokalski's cumulative atomic multipole moments (CAMM) method, 23,29 Stone's distributed multipole analysis (DMA), and more recently, an Atoms in Molecules-based multipole moment method. 24,30 For CAMM, the atom-centered multipole moments are recursively constructed using the density matrix starting from any definition of the atomic charges.…”

Section: Introductionmentioning

confidence: 99%

Transferable atom equivalent multicentered multipole expansion method

et al. 2003

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The transferability of atomic and functional group properties is an implicit concept in chemistry. The work presented here describes the use of Transferable Atom Equivalents (TAE) to represent molecular electrostatic potential fields through the use of integrated atomic multipole moments that are associated with each TAE atom type used in the reconstruction. TAE molecular surface distributions of electrostatic potentials are compared with analytical ab initio and empirical (Gasteiger) partial charge reference models for several conformations of test peptides. Surface electrostatic potential distributions computed using TAE multipole representations were found to converge at the octopole level, with incremental improvement observed when hexadecapoles were included. Molecular electrostatic potential fields that were produced using the TAE method were observed to be responsive to conformational changes and to compare well with ab initio reference distributions. Generation of TAE atom types and their associated multipoles does not involve fitting to sample electrostatic potential fields, but rather utilizes integrated AIM atomic electron density distributions within representative chemical environments. The RECON program was used for TAE reconstruction. RECON is capable of processing 5,000 drug-sized molecules or 25 proteins per minute per 1.7 GHz P4 Linux processor.

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“…These atomic moments centered on atoms have been called cumulative atomic multipole moments or CAMMs [10] when derived from the Mulliken population analysis, although it can also be applied to moments based on any other atomic charge definition as well as on any post-Hartree-Fock, ground state or excited state density matrix. Besides being invariant with respect to translation, cumulative atomic moments can be easily rotated while centered on atoms.…”

Section: Cumulative Atomic Multipole Momentsmentioning

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%

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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Correlated molecular and cumulative atomic multipole moments

Abstract: Perturbation theory of the electron correlation effects for atomic and molecular properties. Second and third order correlation corrections to molecular dipole moments and polarizabilities

Cited by 104 publications

References 63 publications

Dependence of the Intermolecular Electrostatic Interaction Energy on the Level of Theory and the Basis Set

Dependence of the Intermolecular Electrostatic Interaction Energy on the Level of Theory and the Basis Set

Transferable atom equivalent multicentered multipole expansion method

Tracking molecular charge distribution along reaction paths with atomic multipole moments

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