Insufficient description of dispersion in B3LYP and large basis set superposition errors in MP2 calculations can hide peptide conformers

Leo F. Holroyd; Tanja Van Mourik

doi:10.1016/j.cplett.2007.05.072

Insufficient description of dispersion in B3LYP and large basis set superposition errors in MP2 calculations can hide peptide conformers

Leo F. Holroyd
, Tanja Van Mourik

Research output: Contribution to journal › Article › peer-review

Abstract

B3LYP/6-31+G(d) and MP2/6-31+G(d) calculations predict markedly different structures for one Tyr-Gly conformer. Calculation of the energy profile for rotation around the glycine C-alpha-N bond reveals one minimum in the B3LYP profile (phi(gly) = 180 degrees) and two in the MP2 profile (similar to 75 degrees and 280 degrees). Large intramolecular BSSE values are responsible for masking the 180 degrees-minimum in the MP2 profile: approximate elimination of BSSE in the MP2 calculations - by (1) correction using BSSE values from complexes of phenol and N-formylglycine, (2) the application of local MP2, or (3) employing large basis sets (aug-cc-pVTZ/QZ) and density fitting - yields an unambiguous triple-well potential. (C) 2007 Elsevier B.V. All rights reserved.

Original language	English
Pages (from-to)	42-46
Number of pages	5
Journal	Chemical Physics Letters
Volume	442
Issue number	1-3
DOIs	https://doi.org/10.1016/j.cplett.2007.05.072
Publication status	Published - 6 Jul 2007

Keywords

DENSITY-FUNCTIONAL-THEORY
PLESSET PERTURBATION-THEORY
QUANTUM-CHEMICAL CALCULATIONS
AB-INITIO
GLYCINE DIPEPTIDE
GAS-PHASE
COMPLEXES
ENERGIES
DFT
HYDROGEN

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title = "Insufficient description of dispersion in B3LYP and large basis set superposition errors in MP2 calculations can hide peptide conformers",

abstract = "B3LYP/6-31+G(d) and MP2/6-31+G(d) calculations predict markedly different structures for one Tyr-Gly conformer. Calculation of the energy profile for rotation around the glycine C-alpha-N bond reveals one minimum in the B3LYP profile (phi(gly) = 180 degrees) and two in the MP2 profile (similar to 75 degrees and 280 degrees). Large intramolecular BSSE values are responsible for masking the 180 degrees-minimum in the MP2 profile: approximate elimination of BSSE in the MP2 calculations - by (1) correction using BSSE values from complexes of phenol and N-formylglycine, (2) the application of local MP2, or (3) employing large basis sets (aug-cc-pVTZ/QZ) and density fitting - yields an unambiguous triple-well potential. (C) 2007 Elsevier B.V. All rights reserved.",

keywords = "DENSITY-FUNCTIONAL-THEORY, PLESSET PERTURBATION-THEORY, QUANTUM-CHEMICAL CALCULATIONS, AB-INITIO, GLYCINE DIPEPTIDE, GAS-PHASE, COMPLEXES, ENERGIES, DFT, HYDROGEN",

author = "Holroyd, \{Leo F.\} and \{Van Mourik\}, Tanja",

year = "2007",

month = jul,

day = "6",

doi = "10.1016/j.cplett.2007.05.072",

language = "English",

volume = "442",

pages = "42--46",

journal = "Chemical Physics Letters",

issn = "0009-2614",

publisher = "Elsevier",

number = "1-3",

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T1 - Insufficient description of dispersion in B3LYP and large basis set superposition errors in MP2 calculations can hide peptide conformers

AU - Holroyd, Leo F.

AU - Van Mourik, Tanja

PY - 2007/7/6

Y1 - 2007/7/6

N2 - B3LYP/6-31+G(d) and MP2/6-31+G(d) calculations predict markedly different structures for one Tyr-Gly conformer. Calculation of the energy profile for rotation around the glycine C-alpha-N bond reveals one minimum in the B3LYP profile (phi(gly) = 180 degrees) and two in the MP2 profile (similar to 75 degrees and 280 degrees). Large intramolecular BSSE values are responsible for masking the 180 degrees-minimum in the MP2 profile: approximate elimination of BSSE in the MP2 calculations - by (1) correction using BSSE values from complexes of phenol and N-formylglycine, (2) the application of local MP2, or (3) employing large basis sets (aug-cc-pVTZ/QZ) and density fitting - yields an unambiguous triple-well potential. (C) 2007 Elsevier B.V. All rights reserved.

AB - B3LYP/6-31+G(d) and MP2/6-31+G(d) calculations predict markedly different structures for one Tyr-Gly conformer. Calculation of the energy profile for rotation around the glycine C-alpha-N bond reveals one minimum in the B3LYP profile (phi(gly) = 180 degrees) and two in the MP2 profile (similar to 75 degrees and 280 degrees). Large intramolecular BSSE values are responsible for masking the 180 degrees-minimum in the MP2 profile: approximate elimination of BSSE in the MP2 calculations - by (1) correction using BSSE values from complexes of phenol and N-formylglycine, (2) the application of local MP2, or (3) employing large basis sets (aug-cc-pVTZ/QZ) and density fitting - yields an unambiguous triple-well potential. (C) 2007 Elsevier B.V. All rights reserved.

KW - DENSITY-FUNCTIONAL-THEORY

KW - PLESSET PERTURBATION-THEORY

KW - QUANTUM-CHEMICAL CALCULATIONS

KW - AB-INITIO

KW - GLYCINE DIPEPTIDE

KW - GAS-PHASE

KW - COMPLEXES

KW - ENERGIES

KW - DFT

KW - HYDROGEN

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JO - Chemical Physics Letters

JF - Chemical Physics Letters

IS - 1-3

ER -

Insufficient description of dispersion in B3LYP and large basis set superposition errors in MP2 calculations can hide peptide conformers

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